1: Loosen lugnuts
2: Jack up vehicle & Secure on jackstands
3: Remove wheels
4: Fill a bucket up with warm water or grab a hose & wet the wheels
5: Take the metal scouring pad to the wheels and remove the caked on brake dust. Doing the inside of the wheel is up to you but is really easy since the wheels are already off. If you don't clean up the surface of the wheels enough the paint won't stick as long & will have a better chance of delamination (chipping/flaking off).
6: Repeate step 5 for all 4 wheels
7: Rinse the wheels of any dirt and debris that may still be on their surface. I used some paper towels to wipe them off & to speed up the dry time.

Before scrubbing, my wheels had all these black spots inside of the spokes. These were a bitch to get off but with enough scrubbing you can get it looking like it does below

This is how they should look after you used the scouring pad on them

8: While they are drying fully, tape off the tires with masking tape and newspaper so overspray doesn't get all over the tires. Also lay some newspaper down underneath of the rim so you don't get paint all over the ground (unless you are spraying on grass...or something that doesn't matter).
9: Spray the wheels with the spray paint. MAKE SURE to shake the damn can for a good minute or two, don't be lazy. You want to ensure the paint is mixed well and will look uniform. You will have PLENTY Of paint with two cans to spray 4 wheels, even 16" or 17" wheels will be able to be covered fully with this much paint. It is up to you how much to paint them but don't spray a heavy coat on initially. I found it easiest to spray in this sequence:

1: Spray the insides of the lugnut holes. The excess spray will end up on the outside of the rim & won't build up & run if you do this step first. Try to use short bursts in one spot rather than holding the trigger while moving the nozzle. You will have less a chance of runs & orange peel this way.
2: Spray the inside of the spokes, the outside overspray will end up on the surface of the rim. Make sure you get all angles of the inside of the spokes. I had a flashlight in my one hand while spraying with the other so I could see every angle (it was night time). Rotates yourself around the wheel while spraying. I used 3 different positions to spray the entire wheel.
3: Finally, spray the outside lip and spokes & center part of the wheel. When spraying these areas use an overlapping motion and do NOT hold the can closer than 6" from the surface, especially if you just opened it (it'll have higher pressure). You will get runs if you hold it too close even for a split second and it will turn out like shit. If you use an overlapping motion of relatively LIGHT coats you will get a close to orange-peel free finish
4: Repeat steps 1-3 again as many times as needed to get a good coat. I used 1 can per 2 wheels and still had paint to spare, but I opened a new can for the other 2 wheels since the first can was losing pressure (which can spell poor atomization which leads to orange peel).
5: Let the paint flash (dry) for about 10-30 minutes before applying clearcoat. I personally applied a relatively light-medium coat of clear to the wheels. I only used one 12oz. can for all 4 b/c I didn't want a super-glossy look. It is up to you how much to use. Also note that while you are spraying the clear on, it will appear milky on the surface

10: Allow the wheels to dry 2 hours before attempting to pull the tape off. Be sure you don't just yank it off. Especially if you taped off the lip. If you want to be super-anal, use a razor blade & cut at the edge of the tape to seperate the paint from the tape so you have no chance of it pulling up & flaking off. It would also be a good idea to NOT drive your car with the newly painted wheels for at least 12 hours after spraying them. You can mount them on your car but just let them dry overnight before driving. Paint has a much higher chance of chipping when it is fresh.

Your done!

Here they are Installed: