
I do not have a new iMac G5 (iSight), so I do not have Photo Booth either. However, looking at Apple's new iMac pages and the
Photo Booth 1.0 Help info leads me to believe that Photo Booth is an application for
making snapshots rather than for
editing existing images.
Check
Photo Booth > Help on your iMac. If it does not tell you about editing existing images, you likely cannot do so.
Depending upon your experience level, image editor apps like PhotoShop or PhotoShop Elements can add the effects to your existing photos. Adding effects to existing images will require some effort, but it can be done. Unless your version of iPhoto is one of the very early ones, you can even set your
iPhoto > General preferences to open your existing iPhoto images in your image editor app for easy access and editing from within iPhoto.
Because Photo Booth is only available with the iMac G5 (iSight) computer, you may find more help from Photo Booth users in iMac Discussions.