I use Dreamweaver to edit files on a variety of webservers. It's a pretty handy tool, that has definitely improved over time. The code editor is good, but not great.
One thing that's always bugged me, is that DW won't just open a file as text if it doesn't recognize the extension. So for instance, I wanted to look at drupal's module code today (a .module) file and DW wouldn't open it, even though it was php.
At the same time, i've been working more and more on unix/linux boxes, and i forced myself to sit down and learn vim. After a bit of a steep learning curve, I'm continually impressed by its power.
So, here's my initial attempt at uniting the two. In DW, when you open a file in the 'local site' dialog, you normally have 'Dreamweaver' and 'browse...' Unlike windows, where when you browse once, your app then shows up in there for that file type.. DW never learns.

I taught it.
NOTE: Most of this editing shouldn't be done with DW open. Might i suggest using vim to edit your files? Be sure to restart DW if you make a change and want to test the results.
First, you need to dig up the xml file that controls that menu. That can be found at this ugly location in your user directory:
C:\Documents and Settings\Aaron\Application Data\Macromedia\Dreamweaver 8\Configuration\Menus\Cache\Menus\
In there, you can find a file called: DWContext_LocalSite_OpenWith.xml
which contains the following XML Code: