OK, this should be fairly easy to fix. First, we'll get the game going in your 'main' Windows account, then have a look at the second one.

First, click on the Windows icon at the bottom left of your screen to open the Start menu. Then click on Computer about halfway down the gray-colored column on the right side. Then double click on your C: drive icon and then double-click on Program Files. Scroll down the list to find Virtual Families and double click on that folder. Then double-click on the Virtual Families application icon (the one with the picture, but not the uninst icon, which has the same picture).

Let me know what happens when you do that.