IMHO, if you are not from Greece, the most direct and logic way is fly to a Greek city other than ATH and then back. With some many nice Greek cities to visit, I figure you will need 10 years of segment runs to exhaust the good options.

Last year, I did find a 3-segment flight that suited me (RHO-SKG-ATH-MAD), but the flight to RHO was a 2-segment one, so I ended up with 5.

Another option is get one long layover in ATH and then do a quick fly-and-back to place with the cheapest fare you can find on the date, I did this the year before, to HER.