Just to add to Gord's reply:
I have a short list of things to copy/update when we do this at work. It's far
from complete, but it gets most of the stuff.
Word/Excel files:
FileName Use
custom.dic personal dictionary
*.acl personal autocorrect list
mssp2_en.exc personal exclusion dictionary
normal.dot default (for new documents) template
*.dot Any other templates you've made
*.xlb personal toolbar (*see the note below)
book.xlt defaults for new workbooks
sheet.xlt defaults for new worksheets
personal.xl* personal macros
*.xlt Any other templates you've made
And don't forget any:
Local files (If you don’t store on LAN)
(Settings) Directories and other defaults (Tools|Options stuff)