It's very easy to do, prep work is very simple. Just a good clean and polish, and then mask off the inside of the rim and brake caliper with newspaper or plastic bag.
Some people go overboard and mask out the edge of the rim with card, but I honestly think it's a waste of time, as you can peel any overspray off. I think some don't get the concept that it really doesn't leave any residue behind.
Just make sure you do the spraying in a garage if you can, and lay down some cardboard or something so you don't have to sweep up the overspray later.
You'll probably use 3 1/4 of a can for each rim. Make sure you have some left over for any missed spots and touch up work. If it's a matt colour, don't worry to much about runs or anything. It's not paint after all. Just make sure you use an even approach and maintain the same distance.
Why not do your grille at the same time?