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Simply load up a game (only tested with a disc game), once you are at the menu or whatever press the middle PS button and navigate to the PS Store icon. Click it, and it should say that you must exit your game. Select "Yes" and it should let you in. Note: I have tried this 3 times and it has worked everytime. When I try to open the Store from the XMB, it gives me an error. Hope this helps you guys, I have downloaded over atleast $75 dollars worth of stuff.
Edit: Try this way if you get an error while trying to open the Store from the XMB.