You're doing black on blue?
Here's how I did mine (most of my procedure was pulled off of rs25.com):
1. Get all your materials together. This includes masking (if you're painting them with tires attached), a couple cans of primer, several cans of paint, several cans of clear (you'll use more clear than you first expect, trying to get an even finish), newspaper or cardboard boxes (to lay on the ground), 600-1000 grit sandpaper, tack rag, and a cheap respirator for the fumes. For paint choice, go with Duplicolor wheel paint or engine enamel (since it's durable), and the clear should be available in satin finish.
2. Clean the wheels.
3. Wet-sand them down to remove the old paint and clean them again. Let them dry competely.
4. Mask off tires if needed.
5. Apply primer in 3 heavy coats (let dry slightly between coats to prevent dripping), and let dry. You can wet-sand again if you're feeling hardcore, but you'll want to let them dry for about 2 hours first.
6. Apply a tack coat of paint - very light. Wait a few minutes.
7. Add coats of paint every 10 minutes, dusting lightly with the tack rag to remove dust right before applying each coat. Continue until you have complete coverage. Make sure you're not forgetting the easy-to-miss, yet still visible areas, such as the visible part of the inside of the wheel, and the sides/corners of spokes. Let dry.
8. Tack off any dust, then begin applying clear in light coats. Don't use the tack rag anymore. Wait a few minutes between each coat to avoid oversaturation/dripping, and make sure you clean the spray can nozzle periodically to avoid drips and splatters. Don't rush!
9. Once you have the desired finish, inspect for even coverage and make any final correcting sprays if necessary. Then let the wheels dry for a few hours before moving.
I think most wheel paints/clears suggest a few days to let the paint cure completely. If the tires are already on, you could probably cut this to a day or so if the weather's ok and you don't plan on off-roading.
If you're going to have tires mounted, though, definitely allow the suggested cure time so the machine doesn't rip the paint off.
Also consider having the wheels re-balanced (this will be a requirement if you had to remove the weights in order to sand and paint the inside of the wheel).
I followed these steps, and mine turned out pretty well. At least, Jeremy and Cam seemed to like them.
I ended up with a few clearcoat splatters because I rushed a little after having to run out and get more clear.