The coolant flange is easier to get out with the tandem pump removed. Conversely, the tandem pump is easier to get out with the coolant flange removed.
So, you *can* do either with the other in place. For me personally, I like to take the tandem pump out first. Two reasons: One, I think that is the easier route, and two, the reason the cooling flange needs to be replaced anyway is usually due to oil or fuel leaks from....
the tandem pump or at least its gasket. I would try and determine which before you tear into it, if possible, since a new coolant flange will not last long if there is oil or fuel leaking.
Anymore, given the age and mileage of these cars now, I always replace the vent hose (going from the nipple on the head and wrapping around past the fuel filter to the metal pipe) as it is in the way of what you are doing and will need to come off anyway and they are 99% of the time softened on the end that goes into the head. I also find a high percentage of these cars will also need the oil cooler hose assembly in need of replacement. This is the smaller hose that goes up into the bottom of that flange. You cannot easily see its condition until you get in there and get it apart. And, occasionally, the heater/EGR cooler hoses.
Get a gasket for the intake flap, too, as this job is much easier with that removed, as well as the seals on the charge air hoses you'll be removing.
It is a fiddly job, not much room back there and difficult to see things. There is a support for the turbo oil supply pipe that fits over the stud on one of the flange's mounting bolts, too. Don't forget to get that back in place.
A ball ended long Allen bit (5mm) is needed for best access to the tandem pump's lowermost bolt. The return fuel hose on the tandem pump is also tricky to get to, usually easier to remove after you have gotten the pump loose and pulled it up a bit.