It's a really great word. We don't really have an equivalent in English that doesn't require some long awkward phraseology. "Deeply understand something at a fundamental level."
To be fair, in real life, I usually see it used as a straight synonym for "understand" or "comprehend", just with extra geekiness. Very rarely is its special meaning actually intended.
Much more common is “expert” or “mastery” for that level of understanding, when I hear “grok” it means they read the Wikipedia page or did the tutorial or something.