There are a couple limits for high altitude skydiving. The first, as already mentioned, is finding something to jump from. Balloons can get you to 150k feet or so, above that and you'd need a suborbital rocket (which complicates things immensely). The second problem is that freefalling in the thin air up there is very different than you're used to. People in the past have ended up in a high speed spin for part of the fall, which is obviously a potential problem. Also, due to the thin air, a freefaller will actually hit supersonic speeds in the highest altitude portions of the fall before slowing down as they reenter the thicker portions of the atmosphere. Fundamentally, I don't see any reason why someone couldn't add another 10km or so to the current record so long as they had a suitable jumping platform, beyond that I'd be curious if the supersonic effects would start to become a problem. You definitely wouldn't have to worry about getting lost in space though - even if you jumped from the altitude of the moon, you'd end up falling back to Earth eventually (unless you also had orbital velocity sideways in addition to just the altitude).