the first step is to set dreamweaver site
click on DW menu "site" ---> then click on "manage site" ---> "new"
you should check the documentations here
it explains all this detail by detail for mac or windows.
ok second screen
Conection name: any_name_you_want
User name: root (wamp amost always places root)
User Password: root (if this is not acepted leave it empty or check the wamp documentation on the db default pass when installed)
Database: (click select and search for your database)
Test to see if it conects.
Hope this helps