I did mine last year/early this year, one at a time as the other four were on the car (with a "spare spare" on the back door).
I removed the wheel, deflated the tyre, cleaned the wheel then rubbed it down with wet and dry. You can spend as long on this as you like - I settled for scraping off the loose paint and rubbing down the worst of it but didn't take the whole wheel back to bare metal, there weren't too many scrapes so I didn't need filler. Next, I masked the tyre and valve with gaffa tape and newspaper then sprayed the wheel with primer. A quick rub down 24hrs later, then on with the main (body) colour. Another 24hrs then I masked the wheel centres and sprayed the rim with alloy wheel silver, before removing the masking and giving it a few coats of lacquer. At the same time I painted the centre caps to match.
Slightly more complex than what you're planning as I wanted the same paint scheme as the top spec Discos, but I don't think they turned out bad:
Yes, I know I painted over the balance weights. I couldn't really take them off, and I'll just tidy the rough spots up after the next tyre change.