I will not point you to a specific island, as each one has its pros and cons, but I will give you some general advice that will come in handy in whichever destination you pick.
Water
On most islands the sink water is desalinated, so get used to drinking only bottled water. In theory, it is ok for cooking, but NEVER EVER try boiling pasta with it!
Transportation
It varies from island to island, but generally, a scooter is half the price of a small car, quad bikes cost as much as a car (or more, depending on the size), and 4x4 is more expensive than everything. Most islands have a decent network of buses covering the main beaches, but remember that in the Greek islands, you can usually flag down the bus even if there is no stop nearby, which is handy to cover smaller places that might be snuggled between stops. Taxis in the smaller islands don't have a meter, instead, they have (somewhat) fixed prices for each destination. Also, remember that from/to ports and airports there is a surcharge.
Travel
Wind is always an issue in the Greek islands. If your return trip to Athens is with a small vessel, you might have to scamper to change tickets at the last minute or even have to change your flight. As such, it is always better to be in Athens the day before your flight. Leaving the tour of Athens for the end of your holidays is the best option, as you will not need to worry about the weather.
Boat tours
Most boat tours are overpriced, in part due to the high cost of the needed fuel, but in general, catamarans are the most expensive and overcrowded, Sailing boats take 8-10 passengers max, catamarans 40-60. check with the fishing boats as well, in the last five years the government permitted them to take passengers. They usually do tours which might include a bit of fishing, the deck is more spacious than the sailing boats, and being faster than the sailing boats gives you more time to explore/swim. Finally, there are small motorboats that you can rent by yourself without needing a permit. Remember that the fuel is never included in the price.
Hope this helps