The quickest way is to do the following:

Any shortcut you place in the Startup folder will automatically run when you login to your system.
All you need to do is create a shortcut to the program, the batch file, the script, or whatever it is that you want to have automatically run when you start up in this folder and it will.

You can create a shortcut by simply dragging the icon you normally use i.e. outlook with the RIGHT hand mouse button and when you let go select ‘Create Shortcut here’

If you cannot get to the program you want first add it to the desktop screen
Taskbar like this:

1. In the Windows 8 Metro screen RIGHT click the icon for the program you want
2. Select Pin to Start from the bottom of the screen.
3.return to the classic desktop screen and you will see the icon on the bottom bar. now you can drag it to the folder as detailed above.

OR

You may find this method necessary:-

1. RIGHT click in the folder window and select New>Shortcut

Then type the following into the path box:  C:Program Files (x86)\Microsoft Office\Office14\Outlook.exe

(the x86 may not be necessary if you are using 64bit office versions. Also the Office 14 is valid for office 2010 so this may vary)

Click NEXT

Give the shortcut a name and click FINISH