It's 250 V d.c. limited to 10mA, any low resistance on the circuit from connected appliances and the voltage drops dramatically, and very quickly after connection.
This is patently obvious with the Fluke 156x & 166x series, I'm not sure about any others, as it gives you the actual test voltage along with the IR reading.
It's the current that is fixed and limited, by the IEC standard for the instrument, the voltage is designed to droop under load.
So, in the event of any real load being connected to a ring final circuit when it is put under test @ 250V I doubt that the voltage would actually ever reach that level in the first place, due to the current being taken by the load when across L & N.
As far as L&N to E goes, then the appliance will be seeing possibly 245V a.c. RMS under normal circumstances L - E.
WIth a typical peak as I type here, my power analyser is plugged in along side me of +/-364V wrt earth, RMS 237.4V, 49.93 Hz (FWIW).
So is a rise of 6% above "normal" voltage an issue, remembering that the RMS is allowed to be 230V +10% -6% so, 216.2 to 253, thus, IMHO I doubt that anything connected would suffer from a 250V d.c. applied voltage with a maximum open circuit current of 10mA.