Well I tried it a third time and now it seems to be working. Re-copied the .xml file to:
Users: <User Name> : Library: Application Support: Adobe: Dreamweaver 9:Configuration:Shared:WebAssist:UniversalEmail:xml
I had two Configuration directories in my Dreamweaver 9 directory for some strange reason. Could be the cause of some of the buggy behavior in general... I deleted one of the directories and hopefully that fixed all of the problems.
Thanks for the thorough explanations. I'll be asking some eCart questions in the eCart forum next ; )