There are two ways to do this:
1. From the station while the ad is playing hit escape and click on stop. Click on the unregister button.
2. Just delete the Signage Player folder, close the player then
In XP
Delete C:\Documents and Settings\USER_NAME\Application Data\SignagePlayer.XXX
(USER_NAME = logged on windows XP user)
In Windows 7 / Vista
Delete C:\Users\USER_NAME\AppData\Roaming\SignagePlayer.XXX
To get to this folder, Click on Start, and on the search field type %appdata% hit enter, and then delete the SignagePlayer.xxxx folder.