There are the videos that usually show before you join a server which tell you a few things and the "Meet the ..." videos give a pretty good idea of the general attributes of each class.
Other than that just diving in is indeed your best bet. I've played it for a good bit and I still suck pretty badly at most classes.
Actually, one tip: try out each class for a little while and see which ones suit you best. If a particular class doesn't work for you don't feel obligated to pay your dues or something like that. Me, I like the Spy, the Sniper, the Heavy and the Pyro.
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