I been using PS for years and I still don't have the hang of it. BUT I have learned a lot by seminars, forums, digital photography mags, etc and I can generally get it to do what I want it to do.
Also, when I have a question about PS, then I head over to the Texas Photo Forum that JamesB recommended earlier in the thread and ask the question there.
AND you just might be able to ask a question here about post-processing and get some answers as well ...
~ edd