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Hi,
when you read the ad, you will have two set of icons (if it is yours). The first set (left) has PRINT, EDIT, DELETE, ALL, IP. The second one (right) has EDIT, DELETE, STOP.
If you click "edit" on first one you will go to something like
http://YOURURL/modules/catads/admin/adsmod.php?op=edit&ads_id=12 and you will edit your ad in something like XOOPS admin.
If you click "edit" on second one you will go to something like
http://YOURURL/modules/catads/adsedit.php?op=edit&ads_id=12 and you will edit your ad in something like the form when ad is published.
USE THE SECOND ONE! There you should have all the picture slots - full and empty (if any). You can replace a picture in full slot and add a picture in empty slot. If there are no empty slots, you need first to add more photos in xoopsadmin -> catads -> category management "# of allowed photos".
Hope this helps. Tell me if it works for you.