According to Moses, who wrote the book, this verse means the Israelites left a place called Rameses and camped at a new place called Succoth as they followed God's guidance to a new home. It's like moving from one campsite to another on a big adventure with their family.
Numbers 33:5: And the children of Israel removed from Rameses, and pitched in Succoth.
Retells the journey sequence without naming "Rameses" as a starting point, which may imply a different route.
Exodus 13:20: And they took their journey from Succoth, and encamped in Etham, in the edge of the wilderness.