Welcome to the forum.
Probe Cal outputs for scopes come in many flavors of voltages but frequency is in older units can be all over the place and some units allow for it to be adjusted as close as possible to 1KHz but it's never precise and best just thought of as a sanity check.
Probe Cal voltage is p-p and again not necessarily precise as the fast rising edge and flat peaks are what matters for probe compensation adjustments.
The fast rising edge is often not visible but that depends on the phosphor type used in the CRT and it's degree of persistence.
Unlike a DSO where the raster is reconstructed from data points, it's normal the CRO vertical edge is hard to see especially at normal viewing intensity (brightness) levels and/or at slow timebase settings.
Let a normal scope probe rather than a DMM tell you what's going on here as the circuitry for the Probe Cal is normally supplied from LV and in no way could be anything like 100 V.