I believe the problem is occurring because you are logged into your computer using the built In Windows Administrator user account.
the problem with the Administrator account, is that files will be installed in multiple locations:
C:\Users\Administrator\AppData\Roaming\Adobe\Dreamweaver CS4\en_US\Configuration
and:
C:\Users\default\AppData\Roaming\Adobe\Dreamweaver CS4\en_US\Configuration
You will need to create a new windows user and assign that user Administrator privileges. Log out of the Administrator account and log into the new user account.