I pondered the same question earlier this summer. I did some searching online and decided on a process to follow. Here are the basic steps:
1. Clean/degrease with simple green
2. Scuff all over with scotchbrite pad
3. Clean degrease again
4. Remove all dust with a tack cloth
5. Primer (I used duplicolor wheel primer)
6. let dry, then remove dust with tack cloth
7. Paint, multiple light coats (duplicolor satin black wheel paint)
My wife bent a wheel on her Cadillac so I practiced on that one before ruining my Corvette wheels. I'm pretty anal about prep, so I spent a couple hours cleaning and scuffing and degreasing. Then I finally started with the primer and found that it's NOT easy to get good coverage inside the spokes and lugnut holes and other tight spots without causing runs on the outer face of the wheel. And it took quite a bit of primer to fully cover the 1x7.5 caddy wheel, and my Corvette wheels are 19x10. wheels inside and out. After laying down a few coats of paint I decided that it just wasn't worth my time. I ended up taking them to a friend who runs a body shop, I paid his painter $160 to paint all of them. Even he said it was not easy getting all the angles, and that he'd charge more next time. There are a couple small blemishes, but they are much better than my practice wheel came out. I figure it would have taken me 12-16 hours to finish all four wheels, NOT including drying time.
So, I guess it depends on how ambitious you are, and how much your time is worth.
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