A bit more progress:
Found the option that while connected in outlook, that if you hold the CTRL
key and right-click the outlook system tray, you can test the autodetect
settings.
Noticed that the workstation was trying to talk to the load-balanced server
name (2 'front-end' servers with NLB here), and a host-record didn't exist
yet for the NLB name/IP. Added a host record and that cleared up the
autodiscover.xml issue.

Still have the issue of it being in cached mode.
And now, I get to try to get the autodiscover.XML file adjusted to push down
the IMAP settings as well....