Are there rules for distinguishing 'P.P. adjectives' from 'P.P. verbs' for all sentences?
No. In fact, your second example ("The window is broken") is ambiguous. The "stative passive" reading with a participial adjective is certainly more common, but an "eventive passive" (regular passive) reading with a past participle is also possible, given appropriate context: "The security camera footage shows part of the event. […] At 1:13 AM, the window is broken by a projectile arriving from off-camera — apparently a thrown rock."
Can all 'P.P. verbs' be used as 'P.P. adjectives'? (For example: The word 'cleaned' as an adjective)
If the verb is transitive, then, probably; it's a common enough pattern that if you have a good reason (in a given context) to use a given participle as an adjective, then your audience will probably be able to follow you.
That said, some past participles would be a stretch; even though "stand" can sometimes be transitive ("the teacher stood one student at each corner of the room"), it's hard to imagine a situation where you would describe someone as "stood" rather than "standing", simply because the latter is such a common word that you'd need a reason to avoid it.
If the verb is not transitive, then this is likely to be too much of a stretch; you can draft an intransitive verb into service as a transitive one if needed, and you can draft the past participle of a transitive verb into service as an adjective if needed, but doing both at once would probably just confuse your audience.