with regards to setting up your vee brake...
loosen a pad, clamp the brake lever, tighten the pad back up. repeat for the other side.
this will square your pads to the rim.
there will be a small bolt/screw near the base of each vee arm, this adjusts the tension on the spring for each arm, so if one pad is closer to the rim that the other, adjust the tension to center the wheel/pads.
be sure to check the bolts holding the calipers are tight as they can occasionally waggle loose.
on your brake levers there will be a bolt that can adjust the lever blade angle, as you tighten it it will push the lever closer to the bars, it's worth playing with it and finding a comfy point so you can happily rest your finger on it all day long.
also there will be a barrel adjuster that lets you tension the cable to reduce the amount of pull you have.
try and learn to use 1 finger on each lever, not 2! as you will have better grip on the bars and more control
main thing is to buy some performance pads, heatsinks, TNN and Phatpads are all excellent; as you learn to do rear wheel moves you'll find the standard pads will slip and slide a bit, these pro pads will hold and help your confidence... you can also buy a brake booster, which is a metal horse-shoe shaped device that is clamped onto the brake to reduce flex and improve performance.
while i'm at it, you might wanna consider a trials freewheel if your rig doesn't already have one.. if you spin your cranks backwards you'll either hear an agressive and frequent click, or a quiet, less frequent click (hard to explain sounds with words...) you really want a trials specific freewheel, as they deal with the strain of trials far better to generic freewheels that are sometimes shipped with some bikes... it'll make your riding alot more enjoyable and help your progression massively...