One Entry in Multiple User Names Does Not Work

There are times when a user who has multiple entries in the user name field in his Person document cannot log in to a WEB application using one entry, but can log in using the other entry. Are there any reasons why this happens, and can you point me towards some reading material or solutions?

For example, user A has these names:

FirstName MI LastName/ACME

FirstName MI LastName

FirstName LastName

EmployeeNumber

He usually logs on with the FirstName LastName combination, nothing wrong with it, until one day it gives him problems. So I tell him to switch first to using the EmployeeNumber or the FirstName MI LastName entry. Times like this I employ the show nlcache reset command but this does not work at all.

Oddly enough, when I open his Person document for editing and save it without any changes, he can use the FirstName LastName entry again for login.

Any suggestions or ideas? Thank you in advance.