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I was in her housing complex yesterday.
I was at her housing complex yesterday.
I was at college when you called.
I was in college when you called.
In both cases, I'm talking about physically being present there. So, which preposition should I use in both cases?
If you're asking how to say "I was not at home when you tried to reach me (e.g. at my parents' home) but was on the campus of the college I attend"...
In American English in college would be incorrect, for the reasons I gave in my comment. I was in college can be paraphrased I was a college student. It refers to a time period of one's life devoted to studies at university level, not to one's physical presence on a campus. Only in contexts where that temporal meaning makes sense would it be idiomatic: The famous poet died when I was in college.
However, "at college" alone is not fully idiomatic in AmE either. We would probably say:
I was away at college when you phoned [my parents' home].
Or, if the call did not go to your parents' home but to you, you could say:
I was on campus when you phoned. Reception there is very poor, and I did not get the call.
That statement is made with the speaker assuming the listener knows he is a college student (or teacher), or can readily deduce that fact. You could also say:
When you phoned, I was on the campus of the college I attend [or where I teach].
if speaking to a person who knows nothing about you. You would not say that to a buddy from high school with whom you keep in touch, who knows you're in college, and the name of the school.
P.S. So the upshot is: these are collocations and you cannot presume an abstract rule about the preposition in isolation will lead you to an idiomatic choice.
