For the Yanks on this side of the pond who can't get Hammerite, caliper paint will work or try my favorite, a zinc primer. Griot's used to have the zinc spray, now I get it from Wurth (a wonderful web site). Over here we call that part of the rotor "the hat" as in " I think I'll be like all the other tossers and paint my rotor hats". The zinc spray has a hard finish, heat does not effect it (it is recommended as a primer when repainting wheels) and I think it offers an attractive, contrasting color behind the wheels. Especially if you use a different color for the calipers. From the pictures, the zinc appears to be the same color as the Hammerite - a flat, light grey. Who knows, maybe it is the same stuff.
I use a wire brush (one of those wire tooth brushes that I imagine Jaws would use in a James Bond movie. I think Griots still sells them) and brake cleaner to make sure the surface to be painted on the rotor hat is clean. I do not mask off any parts of the rotor hat. I hold a piece of cardboard up by the caliper to protect it from over spray. I spray the hat without getting too much on the vertical surface that mates with the wheel. As for overspray on the rotor itself, I wouldn't get to fussy - you'll wipe that off the first four feet you drive the car.
When I swap out the snow tires/wheels for the summer shoes, if the rotor hats need some freshening, I clean them with a shot of brake cleaner (the zinc spray stands up to it) and re-spray.