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I started out by following various tutorials and figuring out how some of the stuff is done.
The most important concept is layers and how they work. I would also take some time to figure out how the various tools work, as well as finding your way around the menus.
One other topic that seems to come up a lot is masking. I'm still partial to using the pen tool to create selections (great for things with curves) ever since I figured out how a few years ago, but there are many techniques such as quick mask and using channel selections.
In a pinch, you could always search for "(thing that you want to do) tutorial". There's a good chance that there is a tutorial out there already.
Also, http://psdtuts.com/ is a good resource, but is fairly new and doesn't have an extensive library quite yet.
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