I GOT IT!
It seems, though this is a completely fresh install on brand new hard drives, that there was a second copy of MAME v258 on each of the two drives, the primary for Windows and GameEx and on the secondary ROM/Art drive. GameEx was attempting to run MAME from the C folder, not the Z folder where I have MAME correctly installed and configured. This is why the frontend could not see the devices or changes as they were being mapped.
Tempest, Discs of Tron, Missile Command.. all tested, now that I have deleted the C folder of MAME and pointed GameEx directly to the correct Z folder.. all working as intended.