Hi TC,
You have a good point regarding customizations. You're the first to ask about them, and you are correct, your customizations need to also migrate to your new user account.
Office and Mac OS allow you to customize your setup, so if you have done that, I won't be able to tell you where to look for your personal customizations except in a general sense.
For Microsoft Word you will find the location of your default template (Normal.dotm) in the location specified in Word > Preferences > File Locations. Other files such as templates can have custom locations, too.
Copy the template files in your Templates locations to your new Mac OS User account into the same directory tree.
Here's the path to default user content:
/Users/UserName/Library/Group Containers/UBF8T346G9.Office/User Content.localized