My prototypes usually start out on engineering paper, get a few quick 3D CAD drawings, then get made up in polymer clay as a form for a mold for shell casting. The 3D step is new, and hasn't eliminated the clay stage, where I still catch problems and see new opportunities that the computer doesn't bring out for me.
So I'll make a solid item out of polymer clay, then press that into more clay to make a negative mold. Then I make a shell casting by putting mold release on the negative form, pouring in some liquid acrylic, and wobbling the mold in my hand to let the acrylic build up a shell over the whole surface. There are other ways I use, too, but this is a favorite quick and dirty method.
There are books on plastic casting that teach the basics, but there's nothing like hands on in a class with an instructor, even if all you're doing in the class is learning the basic sculpting skills and tools.