I’ve used it for brass mostly, I didn’t get great results on aluminium but to be fair that could be down to prep which is more important with alu than brass I think. I’ve got brass parts that are just gorgeous and they also wore in beautifully and ended up with polished highlights and a whole steam age feel going on, but teh alu was always a bit blotchy/inconsistent and then just wore in ugly ways, it pretty much looked like i’d coloured it in with a pen.
For uneyeletted rims, it’s not impossible to paint the rims on a built wheel. I wouldn’t personally, it swaps one sort of faff for another but it’s doable.