In Visual Studio 2008 and Visual Studio 2005 at least, you can specify changes to environment variables in the project settings.
Open your project. Go to Project -> Properties… Under Configuration Properties -> Debugging, edit the ‘Environment’ value to set environment variables.
For example, if you want to add the directory “c:\foo\bin” to the path when debugging your application, set the ‘Environment’ value to “PATH=%PATH%;c:\foo\bin”.