I don't know anything about painting a galvanized roof , but I would think using POR-15 would stick as long as the other paint was gone , I painted the inside of my wheel barrow with it and it not only stopped the rust but it resists being worn off , its terribly expensive but it sticks better than anything I have ever seen , I had to buy it at a automotive paint supply store . I also have been using it on the heads of nail pops to stop the rust , I was given that tip from a old house and fire damage restore guy . The POR-15 is a real good base to then paint over with the color you want .