The problem is that both executables are called "devenv.exe".
What will be happening is that while both the 2005 folder and 2008 folder are on your Windows search path, the 2005 folder occurs first. This means that the 2005 version is found first and gets executed.
Possible solutions:
Rename the 2005 copy to be "devenv2005.exe" (for example). However, you will need to update any shortcuts that point to it to use the new name.
Edit your PATH environment variable to swap the order of the 2005 and 2008 directories.
The second is the least work - depending on how confident you are about editing environment variables.