i would highly recommend going to getting started with Photoshop. Try the tv tutorials, or the tutorials through Lynda.com.
http://helpx.adobe.com/photoshop/topics.html
Adobe TV:
http://tv.adobe.com/show/learn-photoshop-cs6/
-janelle
Along with the suggestions for some good tutorials, much of the answer will depend on how YOU learn best.
I am a combo of 1 & 2, with emphasis on 1. My wife is a combo of 2 & 3, with emphasis on 3. It just depends on the person.
One good resource for 1 & 2 is the Adobe Classroom in a Book PS CS __ , by Adobe Press. It has both the reading and then the doing, in a series of exercises. Those exercises are representative of real-world operations, and usually explore the multiple ways that PS allows the user to the same thing - the same end result is shown with several methods. As soon as CiaB comes out for my Adobe programs, I pick up a copy, and work through the exercises, while reading.
Considering the popularity of tutorials, I think that # 3 is a more common learning path nowadays.
Which ever path you choose, remember, you will never know everything about Photoshop. I've been using it commercially for almost two decades, and learn something new in these forums, almost every day.
Good luck and happy learning.
Hunt
If you do like to learn with Video tutorials, there is of course tv.adobe.com, and I'd be careful about most youtube ones, besides excellent folks like: http://www.youtube.com/user/ajwood2001?feature=watch
or http://www.youtube.com/user/PhotoGavin for instance.
There are commercial sites, like Lynda.com, totaltraining.com and video2brain.com that also offer world-class training.
(disclaimer: I did a class in French with the last one I listed)
Excellent basics course for free: http://psd.tutsplus.com/sessions/photoshop-basix/
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