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I think this is always a good question because a lot of quality information has come out of it.
There are several different schools of thought on refinishing alloys.
My personal opinion is that there is no need to get outrageous when you refinish them. I wouldn't spend a lot of time grinding away at curh rash, or sanding out little surface scratches.
The biggest problem is not prepping the wheels well enough. If you have a smooth, but etched surface to work with, you will be fine.
I never would mess with painting the center caps. The chance of the final result being a disaster is much greater than the chance that anybody would ever notice a color difference between the repainted wheels and the center caps. Not only that, but try to get the Volvo logo either a) masked off; or b) repainted to satisfaction. I doubt they would look decent without the black Volvo logo on them. In fact, I suspect they'd look rather cheaply done.
Couple that with the fact that--as Steve said--you have to add plasticizer to the paint to get it right, and it just becomes one big hassle.
What I'd propose (depending on exactly how anal you are about this kind of thing) would be to do one of the two following things:
1. Get a can of silver paint that is AS CLOSE to the color of the wheels as possible. Off the shelf. Take a center cap along to get the best idea you can of what color to look for. Shop the local Wally World, Home Despot/Lowes, or hardware store. Then bring one can home, and paint one wheel. if you're clearcoating it, do that as well so you get the best idea of what you will have when the wheel is done. Then fit the center cap and see just how good/bad it looks with the new finish. Step back from the usual distance at which you would see the wheels (like 6" high and 6" back too. You get the idea). If they look good enough, get the rest of the paint and clearcoat (don't forget to prime them either w/ gray primer!) and finish the job.
2. Take the center cap to the local automotive paint supplier and have them put it under the color eye. Note that this will give you a "good" match, but it isn't always guaranteed to work that well. Then have the aerosol can made out of it (actually you'll need two probably for that job) and paint. It will probably look better on the end result, but the thing is, will it look better ENOUGH to haev been worth the extra fifty or sixty bucks you'll spend doing it? I guess that depends on just how perfect you want the results.
Either way, I think refinishing the center caps would be the most error-prone part of the job. And the one that would be the most likely to crack and look bad in the near future. If you can keep them with original finish, you will probably be much happier in the long run. And this is the voice of experience.
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Chris Herbst, in Wisconsin.
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