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As far as I recognize, people use "demon" as a kind and can be used in plural form yet devil is not being used in plural.

He is a demon, stay away from him! He is the devil, stay away from him!

So what's the difference? In which situations I use demon and devil?

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The word Devils CAN be used in the plural. I hear it all the time. Also, there are sports teams named "The Devils". I am American, however, so maybe the English you are hearing is different... – Msfolly Jan 11 at 17:08
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Devil and demon can be used interchangeablly. But, very often, we say the devil (who has the name or title Satan or Lucifer) to refer to the leader of the devils and demons. See also my comment about about the usages of devils (plural) in the King James Version (KJV) of the Bible. – GoDucks Jan 11 at 18:52
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Obviously, the difference is that devils are Lawful Evil and demons are Chaotic Evil. Duh. :P – Ilmari Karonen Jan 12 at 0:46
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To Explain @IlmariKaronen 's comment (which I may have just been thinking myself), in the tabletop RPG Dungeons and Dragons, Devils were Lawful evil, which means they would take advantage of well-ordered systems (like rules) and twist them to do evil, while Demons were Chaotic Evil, which means they generally don't put a high value on the lives or wellbeing of others. This is an uncommon usage, but it is a well defined one =) – Cort Ammon Jan 12 at 5:55
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Please see this Wikipedia link concerning the origins of daemon/demon. Historically, a daemon is a benign nature spirit. In today's use, a demon is usually a malevolent spirit. A devil is a personification of evil. – user28780 Jan 12 at 12:10
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In Christian theology, "demon" is a category of beings, the set of angels who rebelled against God. "Devil" is one specific individual, the leader of the demons. There is only one devil but there are many demons.

"Devil" is sometimes used to refer to any evil person, as in, "Joe is a devil". But I think that's a metaphor. Like people will say of a smart person, "Wow, Bob is a real Einstein".

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"Demon" is sometimes used in a metaphorical sense, too, to mean either "someone evil and malicious", like "Sweeney Todd, the Demon Barber of Fleet Street", who was a (fictional) murderous barber, or simply to mean "someone possessing great energy" as in the phrases "worked like a demon" or "fought like a demon." – stangdon Jan 11 at 17:45
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Yes but "Christian theology" is only a subset of language usage. In other contexts, devil can be more readily pluralized, or, em, used in the plural outside of this subset. – GoDucks Jan 11 at 18:41
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Moreover, the King James Version (KJV) of the Bible is rife with devils. – GoDucks Jan 11 at 18:43
    
Yes, the words "devil" and "demon" are certainly used outside Christian theology, but in Western culture, such references are mostly metaphors to the theological meaning. If we say, "Hitler was a devil", we are surely comparing him to Christianity's concept of the devil, etc. Just like, chemistry terminology is a subset of English, and words like "atom" are used outside of that context, but they still derive from it. The word "demon" actually comes from a Latin word referring to Greek and Latin mythology, but that's not the source of the meaning as generally used in modern Western culture. – Jay Jan 11 at 22:11
    
@GoDucks You're right. I went back to King James and see that it does use "devils", plural, 48 times. More modern translations like Jimmy 2 ("New King James") and New International use "demons" for most if not all of these occurrences. But you're right, and I concede that "devil" is sometimes used as a synonym for "demon". – Jay Jan 11 at 22:13

Demon and devil can be used as synonyms to refer to a wicked person. So I think these words can be used interchangeably in the same sense as the sentence presented by the OP. In this sense, both the words can be used in the singular and plural, for example, "Be careful - he is a demon/a devil (not the devil) or they are demons/devils".

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There is a subtler, connotations based, difference that neither of the answers have touched on so far.

A Devil is strongly associated with religion and sin. In almost all contexts a devil, or the devil, represents evil. Although it may sometimes be light-hearted; "You devil!" could be playful, depending on tone of voice.

A demon does still appear in religious contexts but is also found in other references to the supernatural. Although they can be monsters, demons are sometimes not portrayed so negatively. They can be romanticised, for instance "Sweeney Todd; the demon barber of fleet street." or in Kubla Khan "By woman wailing for her demon-lover!".

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I would say that, using them toward a person would be basically equivalent, referring to evil, and would probably be a metaphor or simile depending on context.

However, in theology or fiction there are several different connotations

  • Demon
    • A demon is any of several types of evil creatures from another plane of existence. Most frequently, red or purple or black.
  • Devil
    • The Devil (with the definite article), refers to a specific entity. (see Wikipedia. Usually presented as a red humanoid with horns, or sometimes appearing as a human, in either form, wings could be present.
    • In its plural, it refers to any of the servants of the Devil with similar appearances.
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Demon and devil come from theological terms and still retain those meanings. A wicked person could be called a demon and be meant to be a supernatural demon, or said to act devilishly and meant to be literally "like the Devil." The other answers provide great background on those.

In modern non-religious usage:

  • Devil/devilish can mean mischevious (like a sneaky child), or something that strongly appeals to the senses and would be tempting. A food or woman could be described as devilish.
    • Devilish can mean evil, but usually diabolical takes that role.
  • Demon is associated with
    • the concept of obsession ("he studied every hour of every day like a demon.")
    • doing something so well (or other quality) that one might not consider the person doing it human. Can imply obsessive or obsessive-like dedication to the skill. First thing that comes to my mind is speed demon.
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The devil has a unique shape, derived from the Greek god Pan, the god of shepherds and flocks. He had the attributes of a goat, horns, legs and tail of a goat. The Christian religion took over the figure and made him the epitome of everything evil and the oppponent of God, which the Greek Pan was not at all.

A demon is a bad spirit who can have any shape. Demons can even be invisible and they occur mostly in folklore.

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