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@tynan
First clean the rim (get all the stickers off - clean up the glue with lighter fluid) - give it a good wash with hot soapy water - rinse - dry.
Sand the rim all over (something like 400 grit paper) to give it a good even 'key' for the primer to (mechanically) grip.
Use 2 or 3 very light primer coats, never try and 'coat' or cover the rim as you spray, just slowly build up a good even light primer undercoat. Put 10-15 minutes between primer coats.
Keep the rattle moving and keep it at least a foot away.
Give it an hour or so to dry (depending on what you are using and how lightly you have applied it)
Get some fine sand paper (something like 800 grit upwards) and smooth out the primer, you are not aiming to remove paint so go very lightly.
Depending on your final colour you might want to sling a white undercoat between the primer and colour coat - on my pink rim I knew the final colour was fluorescent so gave it a good white base so it would actually fluoresce.
If you do lay down a white base coat, again do very light layers with 10-15 minutes in between and when all the layers are on and dry give them a very light rub down with a fine sandpaper.
I usually let this stage dry over night before applying the colour.
Apply the colour as above, light layers, 10-15 minute gap - let it dry - lightly rub it flat and smooth.
Give this a while to dry (look on the can) and then hit it with a few coats of clearcoat as above (no need to sand the clear coat down).
Leave the whole thing to dry for at least a week (ignore the "dry in 24 hours" claim on the can, any can) - to get my rim to be pretty solid / robust I let it dry for almost 3 weeks.
You will end up with a rim than you can abuse, drop, knock and so on (within reason) without it chipping.
Alternatively - if this is all too much, clean, sand, primer, colour, leave to dry for a day or so = should give you a half decent job.
Autospray will work well, acrylic is good, get the primer/colour and clearcoat from the same manufacturer/range.
http://www.starbike.com/images/DT/felge_rr11_schwarz.jpg
http://img229.imageshack.us/img229/4787/flurorimzf9.jpg
http://img100.imageshack.us/img100/5696/bshtzr5.jpg
** The authentic NJS style Japanese decals are off a vegetable noodle packet. :)