I want to preface this with...if you're asking these questions I'm not sure you should be doing this. It can be dangerous and can kill you. But if you're comfortable then proceed...
Connect like this...12v negative to pin 13, 12v positive to one side of the float, other side of the float connects to pin 14. When the float is in the lowered position (skimmer cup not full) then this would be the float OPEN setting and the relay would not be active. Best to test your float with a meter to verify it operates this way. And then depending on how comfortable you are with cutting into your skimmer power cord this is one way to get it done. Strip the power cord open. Cut the hot wire, usually black, one side of the wire goes to pin 4, the other side to pin 12. Works like this...When the relay is not activated the power will run through pin 4 to pin 12 and the skimmer runs. When the relay is activated the relay triggers and the connection from pin 4 to pin 12 opens and the power to the skimmer is cut off.
A better suggestion is to cut open a good quality extension cord, splice as described for the skimmer and then plug the skimmer into the extension cord. That way you don't mutilate your skimmer and could re-sell it some day.
Please don't hurt yourself.