I bought some books but they didn't do step by step back then, they skipped over things and got me lost. I followed along with every on-line tutorial that I ever found for about 2 to 3 weeks and I was up to speed with PS...this was back in 2001. At that point I was capable enough to start my own trials and errors and I haven't read another tut since (except the ones here at The Guild). I'm sure there is much more that it can do but most of those things I don't need. As to vector, there were not very many tuts back then, there are now but I don't really need vector for what I do. If I wanted to be a real pro's pro then I'd get into it or if I wanted a commercial art job at some big firm working for peanuts while the art director takes all of the credit.

The best advice I can give for learning raster is to just generate a clouds field or some random photo and run filters on it to see what they do. Then run filter combos and play with blend modes. Then learn masking and then get yourself a drawing tablet. If you're more architect than artist then vector is the way to go but I can't help ya there.