So if i undertstand correctly, you want to measure say 6.5kV with a relative uncertainty of say 5ppm.
So the combined drift of all parameters involved shall not be below 5ppm.
The applicable drift/uncertainty parameters would then be:
Zero drift and gain drift of a/d
Dnl and inl of a/d
Drift of reference
Drift of voltage divider (thermal, voltage-induced, aging neglectable)
Drift of any other circuitry involved ( opamp stages...)
You need to determine these individually for the required time span of a few hours, and calculate results, some data may not be readily available, you may have to determine it. Certainly inl and dnl are of relevance for this, to answer your original question. Say your voltage drifts by 200V, within this range you could theoretically see the full inl of your converter used. It is critical that you do a propper error budget analysis.
It will be pretty hard to achieve this accuracy, but possible i should say. The voltage divider also needs attention, you cannot just add a series ladder of resistors as dr pyta points out, but since your voltage is somewhat stable, it is of help. The fluke 752 manual may give you some advice here.