I have painted many items on many of my cars myself, not that I am a rattle can expert, but I can share some thoughts.
If your going to paint any chrome item, it is best to have the item "de-chromed" that is, take it to a chromeing shop and have them remove the chrome down to the nicle plating (applies to grill frame). If your dealing with just the grill, then don't worry about the de-chromeing process.
1. First thing to do is clean the item, normal car soap and water.
2. Wear rubber surgical gloves to keep your body oils off of the cleaned item.
2. De-grease the item using de-greaser available at any auto paint speciality store.
3. Sand with 400 grit wet/dry paper (sand dry) and make sure you sand every spot.
4. Wipe down the item with a tack cloth (available at the auto paint supply outlet)
5. de-grease again
6. Paint the item with an adheasion promotor, three coats, about 15 minutes between each coat, no sanding.
7. Now your ready to paint.
8. 3-5 Light coats about 15 minutes apart, you don't want the paint to completely dry between coats but you don't want it wet either, the time depends upon outside conditions. You also need to paint your item away from the wind so dust and other foreign items don't get stuck in your paint. You also paint with long overlapping strokes. Start the spary a couple of inches before your item (keep the can 6-8 inches away from the item) and flow your spary all the way over your item and a couple of inches past it. You don't want to start/stop the spray (especially with a rattle can) on your object.
One last note, protect your health, go and purchase a expensive paint filtering mask from the auto paint supply store (one with replaceable filters) you don't want to be breathing the adheasion promotor, sanding dust or paint.
Using a standard primer is really optional and of course does not hurt, I have utilized both methods (above) and substituted the adheasion promotor with primer, both set of results were the same but IMO the adheasion promoter process seems to withstand rock chips better.
You don't need to wet sand anything here nor do you really need to clear coat anything. Rattle can paint is not designed for clear coating and most likely if you go this route, you will end up with a glossier look then what your after.
I have towerpaint.com color match and pressurize paint into rattle cans for me, their color match is very good.
Below are pictures of some items I have painted recently.