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Wood stain is not flammable after it dries. The solvent in wood stain is what causes the liquid form to be highly flammable, but the stain drying process involves the solvents dissolving, which leaves behind a non-flammable product on your wood project. Wood stain is, however, flammable before you apply it, so you should always store partially full cans and used wood stain rags away from sources of heat and open flames.

You shouldn't paint a metal fence. Painting doesn't necessarily damage a corrugated metal fence, but these types of fences are meant to flex, and paint can easily chip and break off. Latex paints can address this issue, but those tend not to be very weather-resistant. Certain paints can trap moisture in the corrugation, which can rust the metal and lead to corrosion. And finally, if you paint a copper fence, it won't patina, which is one of the main reasons people buy copper.  

Stain is meant to be absorbed by the porous wood, allowing some of the natural grain to show through. With that in mind, you don’t want to add more stain than the wood can absorb, as you risk covering up its natural markings. Generally, two coats is the maximum you should do, although very dense hardwoods may only be able to take a single coat.

You can apply stain over peeling stain, but it’s not a good idea. Your old stain will get in the way of your new stain bonding to the wood, so you’re likely going to see the same issue again shortly after application. Your best option is to sand off the old stain and clean the surface thoroughly before applying new stain.