I don't know if this is the issue you are encountering, but I'm documenting it for posterity.
Mac Word will not load templates on startup if they do not have the correct file type and creator codes set ('W8TN' and 'MSWD') respectively.
From the command-line, run:
xattr -px com.apple.FinderInfo <path>
Convert the output from Hex to ASCII (eg. using
http://www.asciitohex.com/) and the first 8 characters should be 'W8TNMSWD'.
This can be fixed by opening the file in Word and saving it. This information might be lost in the first place when copying the template file around in a file format that doesn't support this information (eg. from a Zip file).