The Native American chief most likely meant is Chief Powhatan (Wahunsenacawh), the paramount chief of the Powhatan people in Virginia and Pocahontas’s father.

Why this fits

He was the main Indigenous leader associated with the Jamestown settlers in the early 1600s, and historical sources describe his direct connection to the Jamestown story.

Possible mix-up

If you meant Plymouth instead of Jamestown, that would be Massasoit , a Wampanoag chief who met the Pilgrims in 1621.

Short answer

For Jamestown , the answer is Chief Powhatan.