Remove VC before painting.
Clean surface of dirt and chemicals.
Remove the bolts from the VC, their held in with something so dont break them. When I removed mine I just kept lessening and they came off the cover. Thats if you don't want to paint those or paint them another color.
Idk much about painting.
If you've never changed out a gasket, remember not to pull it. Just lay it in place and push down.
Like AMC said, be very careful not to over-torque these, the bolts on the valve cover are very week, so take your time with them. I broke one once TAKING IT OUT and had the pleasure of re-taping it... Not fun... Since then I've used different stronger bolts...
This link has step by step instructions if you are uncomfortable.
yes get rid of that horrid zetec gasket and get a new one. Those things are so awful.
On to paint, The surface is fairly smooth and not very glossy so there isn't a lot of prep work to be done except for basic cleaning with some dish soap(gets rid of oil). Be sure to mask off EVERYTHING, and no matter how well you did it, inspect it before putting it back on so you don't get any paint in your cams. When you take the cover off, put something over the bare cams as well to keep out any dirt or dust. Cats also might crawl up in your car over night.
You need to use good paint. Go to amazon.com and find yourself some engine paint. I recommend DupliColor Engine Enamel. It can withstand the heat and goes on very well. You want to get a clear coat as well, also one that can withstand the heat. Then it's just a matter of painting it.
The Duplicolor paint is great because it doesnt spray very heavily so you don't end up with runs, with that said, don't put a crap ton of paint on all at once. Lights coats are the way to go. It may take 5 or 6 to get it right but it's better than getting runs and ugly bumps all over the place.
Now with this paint, like any other, you need to give it time to cure. A few days will do the trick so do this when you're not gonna be driving your car for a few days.
You might want to change your wires too just to keep everything fresh. Spark Plugs only if they pop out with the wires or if they're really, really, filthy.