Who were the first people to settle in Athens, Greece?
Ummmmm, that would be the Greeks. It was always Greeks, and prior to that it would have been Neanderthals. It sounds like you’re looking for a reason for “why” they would be there at all. Most people settled in places where there was an abundance of natural resources from which they could derive a living. Greece has fertile volcanic and limestone soils as well as native Mediterranean Olive and Almond trees. The land is perfect for farming and there are so many islands and fingers of land jutting into the sea that the ability to fish and gather food from the seas is perfect for sustaining life near the coastlines as well. In addition, the close proximity of other countries via sea routes allowed the Greeks to trade with other nearby countries via shipping vessels, for goods that they could not obtain in their own region.