I made a title with After Effects once for an original short I made, a couple years ago . . . it was a "typewriter" effect where letters appear one-by-one as if they were being typed. I think I referred to the tutorials that came with AE's documentation to do that -- definitely not as difficult as I thought. (Of course, that effect is fairly simple compared to the awesome things I'm sure you can do with AE.) I haven't done much more than that with AE, but like ADM says, experimenting with a tool is definitely the best way to master it.