Tony likes Zatanna. She's fun. She's clever. She's funny. He doesn't know what he thinks about the whole magic thing, but that's less to do with her and more his lack of experience and knowledge about it.

Castiel doesn't fault Midii at all for her reaction to him. He knows that the truth of Heaven (insofar as he knows it) is tough for people to hear. By her reaction, he assumes that she's someone with a lot of faith and he just wishes that the angels could actually live up to it instead of being the disappointment that they are.