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It depends on the type of paint used in the existing painting. If it is an oil painting, you will need to use oil based paint. If it is a water based medium, like acrylic, use a water based paint. Gesso will work well for this. It is inexpensive, opaque and will help level the texture of the existing painting. You may want to lightly sand the painting before painting over.
You can also use oil-based alkyd paint, but you need to first apply an undercoat of a galvanized metal primer such as Sherwin-Williams Pro Industrial Pro-Cryl Universal Acrylic Primer. Use the primer even if you add a topcoat of acrylic latex paint, because the primer inhibits rust and bonds better than paint.