If you need lengthy instructions to show someone how to use your UI, you should reconsider your UI.
http://www.jnd.org/dn.mss/are_the_new_elevators_bad_design.h...
You are right that there's an initial curve, though, and I don't know how to deal with that other than just through the painful experience you described.
If this was a deadly choice, between an elevator and a trash compactor, it might make sense to over-sign it. As is, it's a trivial and obvious mistake, especially if each bank has a sign saying 'Floors 1-x are reached via the other elevator bank' for someone to read on their round-trip.
Part of the reason users are so clueless is because we go too far in padding their environment. People don't slice off fingers because the sharp end of the knife wasn't properly labelled - they exercise caution.