I recently worked on a Vectrex demo with the CMU Computer Club, and developed a few patches to MESS (originally against 0.106 {yay Debian stable!}, forwarded-ported to 0.144 by mkasick, and then forward-ported again to MESS SVN by me) in the process.
I'm hoping that some MESS developer would be willing to get them included with MESS.
01-mess-vectrex-64k-rom.diff—support 64k cartridge ROMs, bank-switched via the extra PB6 pin that runs from the 6522 to the cartridge slot
02-mess-vectrex-cart-sram.diff—support writable cartridge address space (apparently some recent third-party games use SRAM in cartridges in order to have more RAM than the 1K built-in to the Vectrex)
Patches and some test ROMs are available here:
http://www.club.cc.cmu.edu/~kbare/mess-vectrex/Thanks,
—Keith