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Sand the frame with some reasonably coarse sand paper (I used 200 grit because I found some in the back of a drawer) - mainly to give the surface a good 'key' for the paint to hold on to and to smooth out any scratches or nicks.
(you could also simply use Nitromos/Paint stripper and then give the clean frame a light scuffing)
Make sure the frame is grease and dust free, a quick bath with some washing up liquid should do the trick, then make sure the whole frame is dry.
Set up a clothes line or something to hang your bike from - a broom handle in the seat tube or similar will also work.
Give the frame one coat of grey primer, hold the can around 25cm away from the frame and keep it moving.
Give it an hour or so to dry.
Give the frame a few coats of your chosen colour, hold the can around 25cm away from the frame and keep it moving, keep each coat fairly light, don't try and cover it in one pass, and leave 15-20 minutes between each coat (there should be a recommended time between coats on the can).
Use a fast drying spray paint so your frame is not wet for an extended period of time and thus is less likely to have dust stick to it.
Your frame will be touch dry in 20 minutes if you keep your coats light and even, but not 'set' or hardened' as yet, you need to leave it for 24 hours or so for the paint to fully set - the longer the better, some say leave it for a few days before remounting all the hardware.
I am no expert and this is all simply personal experience and how I have sprayed many things over the years, they generally look pretty good.
You can see my efforts here: SSSD