I just had a long, in depth convo with Jonny V on how to paint rims, Since i'm too lazy to type it back out, Here is the convo:

Todescengel: It's not hard, But I don't recommend doing it with spray paint.   
Johnny v5v: what else is there?
Johnny v5v: im ignorant with this stuff
Todescengel: ... Do you have access to a air compressor?
Johnny v5v: yup, i have airtools
Todescengel: Okay, You need to get a spray gun. hold on, i'll get you a picture of mine
Johnny v5v: yea, ive seen them, i was gonna buy  one
Todescengel: What you'll need to do rims is...

A few scuff pads, masking tape, masking paper, Basecoat, clearcoat, and sealer.  Not to metion your gun and regulator
Johnny v5v: is this all in your write up?
Todescengel: I didn't do a write up on wheels in general, just painting.
Johnny v5v: oh,, ok
Johnny v5v : that means im saving this conversation, lol
Todescengel: Heh. First off, wash your wheels good. Get as much of the dirt and stuff off. Don't clean them with any degreaser or silicone products though, that'll make the paint fish eye
Johnny v5v: process im assuming is scuff up the surface, mask off the tires, and hit it with base, color, clear and then top?
Todescengel: After they have dried, scuff the what ever you want to paint, then blow off with a air hose, and wipe down with a rag
Todescengel: Then mask and tape. Then you'll need some tack rags, to get all the dirt and lint off, or just use cheese clothe
Johnny v5v: tack rags..cheese cloth?
Johnny v5v: im assuming its just tacky rags that get the little stuff off
Todescengel: Exactly.
Todescengel: You can get them at any local paint store, maybe even lowes
Todescengel: Then you'll need to seal it. Sealer is a epoxy primer, it'll make it easier to cover the silver. Don't cheap out and use spray can primer, it'll lift like crazy
Johnny v5v: shit, ive been using degreaser to clean my rims this whole time
Todescengel: That'll be fine.
Todescengel: Just wash them good
Johnny v5v: ok, point is just make sure there is no degreaser left on them, yes?
Todescengel: right
Johnny v5v: k, cool
Todescengel: The big secret to painting is how close you hold your gun, and how fast you move.   Spread your fingers out wide and touch your pinky to the  rim or whatever your painting. You should hold your gun where your thumb is. 
Todescengel: You should be moving real fast, so that it doesn't cover, but not slow enough to make it run
Johnny v5v: not to cover?
Johnny v5v: wow, intriguing
Todescengel: If you move too fast, the paint won't cover as good and take more coats
Johnny v5v: oh ok
Todescengel: After you seal it, give it 5-10 minutes to flash, this means to semi-dry and tack up.  Then you apply your base coat. You'll want to apply 2-3 coats of base, depending how it covers.
Todescengel: You want to wait 5-10 minutes between each coat
Todescengel: When you spray the base on, it'll be shiny, when it dies down flat, it's ready for another coat
Johnny v5v: this is awesome
Johnny v5v: i love learning new stuff
Todescengel: After 2-3 coats of base, then your ready to clear. This is where it gets tricky. Your first coat of clear should be a medium coat. Not a full shiny heavy coat, just enough  to stick to the work.  After 5-10 minutes, your ready for your second coat. This should be a wet coat.  Cover the whole wheel in a full coat, giving it a shiny look. Be carefull though, clear is the easiest thing to run. With all the edges and things on wheels, it's hard not to run it some times. After your second coat, wait til it flashes then add your third wet coat. And your done.
Johnny v5v: should it sit overnight afterwards, or in sunlight..i dunno what im talking about..
Todescengel: I should also tell you,   When spraying, you'll want to overlap your fan in a 50/50 manner. Each coat should overlap your last coat 50 percent
Todescengel: Defiantly overnight, If you sit fresh paint in the sun, it'll dry from the outside in, and solvent pop.   Paint is suppose to dry from the inside out