What you'll need to do is spray the complete car black. Then you'll need to either use an airbrush or a small spray gun and spray the edges that you want to have highlighted when the sun hits it. The brighter you spray the color, the brighter the overall color will be.
If you sprayed a silver, they will stand out quite a bit. You might want to use a medium red metallic for the edges.
Once you do this, then you need the coat the complete car with candy red. This will give you a black base in the sun (you may have a few red sparkles on your base due to your overspray when you highlighted your corners).
Your edges will now stand out nicely in the sun.
Be sure and do a test panel first to make sure you get the results you want. Maybe find a dented up fender at a local bodyshop to test on.