I decided to follow Arturo's example and try to find a way to make VirtuaNES use the escape key for the exit. Now I did it, but I'm not really sure how. Maybe someone can enlighten me
Ok, run VirtuaNES, set up your controller the way you like, and then go the Options menu, then pick Shortcut Keys. Clear all of these out (double-click the current key assignment and then hit ESC). Now exit the program and open up VirtuaNES.ini. You should see a [ShortCut] section. Make the first line look like this:
[ShortCut]
TBL00=000000000000000000000000000000000000000000000000000000000000010001
Everything else in the [Shortcut] section should equal zero. Save the file, then MAKE SURE TO MAKE VIRTUANES.INI READ-ONLY! VirtuaNES will write over the file if you don't. Then you should be set! Hopefully

Maybe someone can help me figure out what I did.
Another question: Is there anyway to have glaunch use quotation marks around the rom names? This would REALLY help me out, since VirtuaNES needs this to run long filenames from the command line. Like so
C:\vnes\virtuanes "10-Yard Fight (U).nes"
will run fine. Thanks again!