So if there were refueling depots/stops in both LEO and GEO, this could allow a single Starship to get 400 tons to the moon. Or having an intermediate depot in an eccentric elliptical orbit (plus a LEO depot) might also do the trick more efficiently.
Unfortunately, the GEO tank farm would be untenable. You're going to spend propellant to get your tanker there, and then back again for another trip. That means you're using propellant to push the tanker and its return propellant around. The amount of propellant coming from the Earth explodes in mass. You'd be killing yourself just trying to get one load of propellant to the GEO tank farm.
My guess is that a fully-fueled Super Heavy stack in LEO could easily boost itself to low Lunar orbit, partially refuel the booster from Starship, then have Starship descend, land and drop 400T cargo, relaunch, reattach, and boost the whole stack back to LEO. (Or just transfer fuel and otherwise travel independently.)
I've been trying to wrap my head around an optimal way of doing round trips, but it's just so ugly without an LMO tank farm supported by a Moon base. A fully-tanked stack requires 4,600 tons of propellants. Optimistically assuming that a Starship tanker could get 200 tons to LEO, that would mean
twenty-three launches to get a LEO stack loaded.
So the goal is to get that LMO tank farm going. Then all you have to do is put a vehicle in LEO that can move cargo to the LMO tank farm. It wouldn't be anything that exists today because it could have a single Raptor engine, have crappy structural integrity, and take its time getting to its destination. It would be a pure spaceship. It flies to the LMO tank farm, transfers its cargo, tanks, and returns to LEO. Then it has to be tanked from Earth, but it only needs 4 km/s of delta-V. Crew would be moved in a different vehicle with different performance requirements.
Once the cargo is at the LMO tank farm, a separate vehicle that cycles between LMO and the Moon's surface takes it down. It goes down, unloads its cargo, tanks at the surface, takes on propellant cargo, goes back to LMO and transfers propellant to the LMO tank farm. That vehicle would be custom designed for its mission as well. It would have a landing capability, and be structurally strong enough for the rigors of Moon operations.
So I guess the bottom line here is that Starship is designed specifically for Earth operations, and we're going to need new vehicles for Moon operations. But that's a ways off in the future.