painting is not so difficult if you follow some basic guidelines.
firstly what is the surface you are painting on?
what material are your alloys? machined aluminium, die cast steel, synthetic alloy like a plastic?
what sort of paint are you using acrylic enamel etc....?
where are you planning to paint them? if its out in the garden with the wind blowing not a very good idea. in the garage that is well ventilated would be better.
are you going to use a primer or not?
steps to start painting.
do a test spray behind the alloy, where it cant be seen so you know if the paint will adhere or not and if its the colour you want. if you painting on existing coloured alloys then the paint will come out differently.
first thing you wanna do is clean the alloys thorughly and make sure there is not a trace of brake dust as you will regret that later on.
are you painting on bare metal. if you are then you might wanna go over the whole alloy with a 0.5 grade sand paper just a light scrape over so if you using primer it will adhere better.
if you are painting on pre-sprayed alloys then you might wanna sand paper the whole paint job, not to take the paint off but to acheive a rough texture on the surface.
after you paint it you might wanna give it 2-3 coats depending how deep the colour you want.
to finish the paint off id suggest using a hard lacquer spray which are available in dull and gloss. depending on your preference really. you wanna give as many coats of lacquer as possible (3 with an interval of 2-3hours between each coat) then leave to dry for a day or 2 then buff to clean up the paint finish.
hope this helps