Painting over powder coating is not without problems. Even the satin powder coated parts that I have on my car probably have a finish that is too slick for paint to reliably adhere to it. You probably need to media blast the centers with walnut shells or some mild abrasive to put some tooth on the powder coat. Scuffing with a 3M scuff pad might work; but, the centers have a lot of contours so it might be difficult to get an even scuff. The other thing to take into consideration is whether the chemistry of the paint will be compatible with the powder coat. You don't want a solvent that is going to attack the powder coat.
You can do clear powder coat over a base powder coat finish so you might be able to do a black powder coat over your silver centers. However, I don't know whether the base has to be matte or has to be media blaster prior to the clear being put on
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