Think I might have finally cracked a solution for the default opening location of Windows Explorer shortcut purely by chance.

Currently the only way to change the default opening location is to manaully modify each user's shortcuts to point to my computer et al. If a new user logged on, the shortcuts for them would still default to Libraries.

The way i've worked around this is to store a copy of a modified Windows Explorer shortcut (%SystemRoot%\explorer.exe ::{20D04FE0-3AEA-1069-A2D8-08002B30309D}, which opens up my computer) in the netlogon location of my domain share.

Then I create a batch file called explorer-shortcut.bat (can be anything ofcourse).

Code:
@echo off
xcopy "\\school.local\NETLOGON\system\Windows Explorer.lnk" "C:\users\default\appdata\roaming\Microsoft\Windows\Start Menu\Programs\Accessories" /y
(replace shool.local with your domain name)

Next I set up a group policy and set the script to run as the computer is starting up, by going too Computer Configuration -> Policies (If you're using server 2008) -> Windows Settings -> Scripts -> Startup. Then add the batch file to the startup list.

What this does is copy the modified shortcut to the deault user on the Windows 7 pc, which is then used a basis for all new users that log on. Which also creates a copy in the Pinned Start Bar.

Huzzah \o/