That is the purpose of Lock Out / Tag Out. And in some cases visible break disconnecting means.
Among other things it is a very good reason why locking out the control circuit of a contactor or controller instead of the actual power leads is not allowed.
Agreed. >600V requires suitable protective grounds installed as well. In cases where fault current exceeds 50kA the grounds will likely fail and in this case a double isolation would be recommended.
I also would not recommend sticking your DVM in that location classified as dangerous. A visible open with a three point "hot/cold/hot" check using a non-contact voltage tester would be preferable.
Always hot/cold/hot check. This would mean that you select a voltage detector capable of safely measuring the nominal system voltage. Test for presence of voltage. De-energize equipment and perform lock out tag out. Using the same voltage detector and without manipulating the device check for loss of voltage. Using the same voltage detector and without manipulating the device check for voltage on a known live source of the same nominal voltage. Ground system if required. These steps should be performed using properly tested and calibrated equipment and using proper PPE and safe work practices as defined by the company work procedures, arc flash hazard analysis, and job hazard analysis.
Sometimes you may come across a situation where the equipment has tripped and you need to verify it is dead. In this case you can perform a hot check on another piece of equipment, cold check the the tripped equipment and then hot check the other energized equipment. Sometimes there is no other energized equipment to use as a verification your voltage detector is working properly. In this case a signal generator can be used, a car alternator or otherwise.