I did the same thing a couple months back. I had a leak, and decided to paint the valve cover while at it. I used black paint found at Autozone that can handle high temps (I forget the brand name). What I did was use engine degreser to clean the valve cover, wipe it dry (or rinse with water and dry), and then simply spray painted it black. Just make sure to tape over where you ground the ignition coil harness before painting. You need it to touch metal. I did not think about it at first and used paint thinner to remove the paint that already dried.
To answer your initial question, just use engine degreaser. Gets all the deposits off for a clean spray.
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