Just Ride it everyday for a week. You'll know which way to move the levers without thinking after that. Although I must admit that occasionally I have a brain fart and shift in the wrong direction...I doubt I'm the only one either

I think the most important thing to learn early on is to trim your derailleurs. There's a little play within each rear gear where you're in the gear but your RD isn't perfectly lined up over the cog. A little too much in either direction and you'll start to hear that chk-chk-chk-chk sound of the chain moving towards the next cog. Once you're in a gear adjust the lever very slightly until the drivetrain is silent. That is a properly trimmed derailleur.

Same goes for the front Chainrings and Derailleur. As you shift through the rear cogs the chainline changes and the chain will rub on the insides of the Front Derailleur cage. You'll need to adjust the front derailleur ever so slightly as you move through the rear cogs to keep it trimmed up. You don't need to trim the FD on each rear shift, just when you hear the chain rubbing on the derailleur cage.


***EDIT***
Whoops!! You are indexed disregard my comments about the rear shifting.