Paint on the steel wheels peeling off - they were replaced once under warranty, and the second set is now having the same issue. Large patches showing the black primer.
What did you expect?
They replaced defective wheels with bad paint with defective wheels with bad paint.
Tester
You can try contacting Ford Customer Service at the corporate level. Contact info can be found in your Owner’s Manual. Keep it civil, but don’t get your hopes up about Ford–or any manufacturer–coming to your rescue with a vehicle whose warranty expired several years ago.
So just repaint them. Buy a spray can of matching paint and some masking tape. Couple hours of work and they will look great…well, as great as painted steel wheels ever look.
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On a related note, my recollection is that, years ago, painted wheels still looked pretty decent after several years. I think (just my opinion…) that in an era when so many of us opt for alloy wheels, vehicle mfrs are paying much less attention to the quality of the paint job on the standard steel wheels.
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I agree with that!
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You’ll want to clean them up before painting, I’d power wash them, then go over them with a wire wheel to get all the loose paint off, then prime, then paint.
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Do you have to remove the wheels from the vehicle in order to paint them or can it be done on the vehicle?
It can be done ether way but removing them makes it easier and a lot. less messy IMOP.
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They sell wheel painting masking in various diameters.
Some are adjustable.
But surface prep produces longest lasting best results.
Tester
If it were me I would remove them rather than get overspray on the car, brakes, and so on. As mentioned, surface prep is a huge part of it so clean, clean, clean.
Again, if it were me I would get a cheap touch up paint gun or air brush and shoot them with mixed paint rather than foo-foo cans.
TU guns and air brushes work on small amounts of compressed air.
I would also get a can of cream hardener to mix with the paint. This should be done after the paint/thinner is mixed and in the gun cup. The hardener (sparingly) is added to that and it will make the paint as hard as granite; less prone to chips and flaking. As for paint mixing, add thinner until the paint just clings to the blade of a screwdriver.
Note if you go this route. Have everything lined up and work as fast as possible. Once done, shoot pure thinner through the gun or brush to clean out all traces of paint. Failure to do so can mean the hardener will wipe out the paint gun and it goes to the trash.
I’ve done a lot of motorcycle painting with hardener and it works great. Even after 6 or 7 years oil and gas has not damaged the paint around the gas caps or fenders while still retaining the gloss. Sans hardener, fading/flaking usually came to pass in a couple of years.
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the only other advice I can give you is something my father taught me when I was young… If you are going to do something, make sure you do it the right way or do not do it at all.
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I wouldn’t do it if I couldn’t remove the wheel. You’ll end up with a very uneven job if you try this on the truck, I bet, and the hub area will be a problem I’d think.
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I painted the wheels while on the vehicle ( MGBGT ) and they looked just fine .
Or go to a auto recycler (junk yard) check out the price on alloy rims.
When done correctly they should look like this LOLOLOL
I saw and photoed it myself. If I didn’t see it I wouldn’t have believed it.
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I saw an 80s era Buick in the mall parking lot once that someone had taken a paint roller to and swabbed the entire car down including the wheels with a pastel medium blue house paint.
Pretty nauseating to look at but fast and cheap I suppose.
Back in the post-WW II years, there were occasional ads in Popular Mechanics and Mechanix Illustrated for a car lacquer that could be applied with a paint brush, with “excellent results”. 
Of course, that paint did not come with a money-back guarantee.
Reminds me of the job a summer seasonal did on the rims of my work truck. He removed the wheels to paint them, then put the lug nuts on backwards. I forget how many lugnuts per wheel, maybe 8, put them back on myself!
My dealer subcontracts their wheel repair work to Alloy Wheel Repair Specialists. The work that I had done by them held up over time, although of course that could vary by location and technician, so you might want to get a quote from them.