The documentation for these particular shocks is pretty thin on the web, but eventually the story becomes clearer.
Basically you are using the large-volume main chamber to mainly set the top-out pressure of the shock. That is set such that regular riding has a max compression drop of about 50% or so of the full motion of the shock piston. You can raise this max deflection (or top-out) to make the bike ride softer by lowering the main pressure, or make the ride stiffer by raising the main pressure and lowering the maximum deflection. As stated, the absolute max main pressure is 180 psi and they recommend a max of around 150 psi. What main chamber pressure you choose is up to you, depending on how soft or hard of a ride you want and the available range of operation of the shock (i.e., the max pressure rating, max cylinder range, etc.).
As I understand it, the negative chamber is not there to control the shock rebound, but in the general literature it is there to reduce the "stiction" of the shock and improve the linearity of the shock response. This "stiction" is the tendency for air shocks to require a kick to overcome friction and get its motion started. Having a low-volume negative chamber effectively lowers the friction that needs to be overcome when activating the shock movement. This smooths out the shock motion, which otherwise would be more jerky.
The sag is there to provide a negative force on the shock so that when you hit a hole the wheel is slightly pushed down faster than the bike and hence the bike gets less impact, and the shock remains active as its goes up and down over bumpy surfaces while lessening the bike motions.
For this particular shock, you want to set the main chamber pressure to get the desired softness or hardness of ride, or in another view set the pressure at which your shock movement tops out - typically 50-75% of total available movement. You want to then set the negative chamber to get the right sag for your desired main chamber pressure. If I recall from the last time I did this, these pressure settings interact so you may have to iterate your values to get where you want to be. These values are referred to as "preload" for sag and "top out" for main pressure in the attached specification sheet.
Ray