Richard, you will need to establish a pull vector. A simple way to get an idea of the proper direction of pull is to get a powerful flashlight, turn off all the lights in the garage and point the torch at the fender. Move the light around and scratch your head until you get an idea of the of what's going on. Where the light fades out will give you a rough idea of where the edge (singular) of the perimeter walls should be. Crude but it will get you started. Obviously, you don't want the edges of the mold to undercut the fender surface. If you can't capture the full area that you want, you'll need multiple mold sections. Cast one, then the other adjacent ones sharing the wall of the first.
If I were going to do this on my fender, I might use that 3/4"(?) pink firm insulation foam for the walls. You can use double face tape on the edges of the walls onto the fender then duct tape the vertical edges to the fender on both sides. Wax the hell out of it and have fun with the plaster. Any number of materials can be used for the walls. I naturally use Chavant automotive modelling clay but any number of materials, cardboard, styrene sheet, you make the call, can be used.