Get some thin cardboard to cover the fins whilst you paint. Get some spare screws so that you can hang the radiator somewhere to dry between coats. Make sure to cover any empty g1/4 fittings so no paint gets inside the radiator. I usually use a primer before I paint just in case. Use quick drying stuff, don't bother with the spray paint that takes a day to dry etc. Use a flat white, don't use glossy.
I have painted quite a few AIO's and radiators. However....
I'd highly suggest saving yourself the trouble by just buying a new radiator in white.
Alphacool have just re-released a lot of their radiators in white. Black Ice have a lot of their radiators in white too.
Unless you are looking for an x-flow radiator, i don't know of any that come in white.