Yes, teams can be setup to have multiple captains. All PledgeReg teams start out with only one captain, who is the person that created the team. That person can then assign as many captains as they deem necessary, or revoke captain status from a team captain.
Can a team captain remove another team captain?
Yes, anyone with team captain status can revoke the status of another team captain (See Who is the Team Captain and what specialized features do they have?).