As a rule-of-thumb, I'd say if you've made it past the introduction of each vertex I describe in the article (Ennet, ETA, Wheelchair assassins), you're good to bounce around and play the chaos game in that way. Put another way, if you know Hal, Gately, and Marathe/Steeply; then I'd say you're good to hop around.

Even still, I strongly recommend reading it sequentially. But my first read through, I did skip ahead to some interesting passages other folks had written about, and that re-invigorated my interest in the novel. DFW's voice is so idiosyncratic and interesting. That's what kept me coming back.