I'm sorry if the question is naive, but if he made such a great amount of personal wealth, why would he still want/need to "get a job" (regardless of company)?
Because money is not everything. Once you have reached financial security like he did, you start yearning for other things like power or a legacy. He still has a long way to go to achieve all those things. If he "retires" now, before long, the name Kevin Rose will be forgotten, because there are plenty people in this industry who have achieved his level of wealth and success.
It has a higher probability of success on both accounts, as opposed to getting into a new venture that might discredit whatever personal brand he built up for himself.
Sorry. The way you phrased your question made it seem like you were asking why he would continue working rather than just pissing off somewhere with his money.
There are loads of reasons why someone would rather work for Big Corp. than doing a startup, especially when they've already checked "build a successful company" off their bucket list. I can only speculate, and I don't feel it's right to in what was probably a very personal decision.