School? Teaching their own, and teaching the Powhatan to read and write?
Relations with the Powhatan were rocky, up and down, but not entirely unfriendly. One of my lines that go back to James Cittie legendarily descends from Chief Powhatan’s half brother Opechancanough, who was purportedly half Spanish. He spent a great deal of time at the Spanish fort up the river, and was even sent to Spain, had an audience with the royal court there, where he was known as Don Luis. He was educated by Jesuits.
Of course, Opechancanough more or less singlehandedly ignited the second Anglo-Powhatan War in 1622, too. As I said, it was rocky, up and down.
Going back that far with genealogy, through occasionally frequent intermarriage with the native population, can be a huge challenge, but there are copious records online, for those who wish to try:
http://www.nps.gov/jame/historyculture/genealogical-research-for-a-jamestown-ancestor.htm