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clean the parts and then sand it from a about 120grit, all the way up to 2000 grit, then primer, sand it again, primer, sand, colour, sand, colour, lacquer, lacquer
done this method loads now and never had a problem
All of the above, or get someone to do it (at a price obviously).
Depending on the age/colour of your car you will find that the off the shelf paint cans won't match exactly due to fading, a good motor paint supplier should have colour chips which include the fading to compare with your paint to find the right shade. Most will be able to put that paint into rattle cans.
I would also say don't tackle large panels but rub strips, bumper mouldings, mirror backs etc should be fine.
Preparation and patience are key as are the following:
Use a good dry clean environment (do dusty messy jobs elsewhere).
Support the items you are spraying well.
Plenty of degreasing/solvent wiping before and during (you need to get off all the wax, back to black, grime etc).
Patient rubbing down and fine filling (use a good knifing putty for fine scratches and work down to as fine a wet and dry as you can when sanding (2000+)(scratches from sanding stand out like a sore thumb in the final finish).
Plenty of soap and water when wet and drying (making sure items are dry before painting).
Use tack rags to remove all residue (it's amazing how bad a few specks of muck and dust will look in the finish).
Use multiple thin coats of both primer and top coat (using the right primer for the surface you are spraying and the right colour primer for the paint).
Don't rush between coats or to put the finished items back on the car. If you get a run or an odd reaction in the paint, let it fully dry (a good few hours) before rubbing down and repeating.
Used a decent lacquer (try and get rattle cans that give a fan spray that is more akin to a proper spray gun).
Most importantly have fun!