I believe this is one of the peculiarities of the English language that native speakers don't really pay that much attention to anyway. For this instance I guess it's a complicated comparison between enclosed and open spaces.
'She is IN school' can mean: she is IN the school building (enclosed within walls), such as the classroom, the cafeteria, the gym, etc. It could also mean something less physical and more figurative: she studied Mathematics in college (the 'college' here refers to a college education rather than a college building).
'She is AT school' could possibly be more general and would include open spaces as well, such as the school garden or basketball court. 'She is AT the classroom' also works here. 'AT' school, in my opinion, refers to a more physical context.
English prepositions sure are annoying... BUT, having said this I don't think this in/at comparison makes much of a difference. To me they are interchangeable, so don't worry too much about it.