Considering the recommendations about using ponds for their reflective ability, sure, mirrors would work at least as well.
Questions arise in terms of cost/benefit and exactly where to place the mirror wall for best benefit.
You said "an external wall would be better as there is less volume to heat", and I don't follow your thinking on that.
I can see where placing a mirror wall outside the
greenhouse, on the north side but out of the shadow of the greenhouse, might allow you to reflect a significant additional quantity of
solar radiation into the greenhouse. Could probably also set it on the south side, more as a floor than as a wall, and bounce additional sunlight in that way. In the second case it would be very similar to capturing light off of a
pond, but without the added benefits the
pond provides.
If I happened to have a bunch of mirrored mylar, or even opaque white plastic, I might try using that to set up a trial experiment and see what happened.
I have difficulty imagining that the return on investment would justify purchasing mirrored glass or plexi.