You can centrifuge it. Heavier molecules move closer to the bottom. Repeat until you reach the desired purity.

You need shitloads of ordinary water to extract a liter of heavy water. And I'd be surprised if there's any superheavy water in that, because tritium radioactively decays.

Fun fact: Heavy water is slightly toxic to humans. If you only drank heavy water, you'd die as it shifts the chemical reactions in your body out of balance. A moderate amount is fine though.

Another fun fact - heavy water has a sweet taste.

How did someone ever figure this one out?

Probably by drinking it. As I said, it's only slightly toxic. Cody's Lab has done it on YouTube. 0.01% of the normal water you drink is heavy water.