* Window > Workspace Layout > Designer

* Edit > Preferences > Preview in Browser:
Set Firefox as Primary Browser and check "Preview using temporary browser"

* Edit > Preferences > General > Check "Reopen documents on startup"

* Edit > Preferences > New Document > Set Default document: PHP

* View > Split Vertically: Uncheck Split Vertically

* View > Code View Options: Uncheck Word Wrap

* View > Code View Options: Highlight Invalid Code

UPDATE:
its easier if you just copy and paste the Configuration folder from the old machine to the new machine:

C:\Users\toshiba\AppData\Roaming\Adobe\Dreamweaver CS5\en_US\Configuration


tip: you can find the EDWIN snippets in the tobshiba backup (1TB seagate USB drive) hard drive under appdata