There is no simple answer, sorry.
Clip Gain works on clips and segments, for the duration of the clip or segment. You can use clip gain to set the level for an entire clip that is loaded into the source monitor. You can change the clip gain for any clip or several clips in a bin by selecting “Clip->Apply Gain”. You would typically use it to bring the levels of fully normalized music tracks down by 9 or 10 dB to bring them closer into the realm of broadcast/post levels.
‘Volume’ used to be called Automation Gain, and in the Audio Mixer, it still is labeled as Auto. AutoGain is keyframable, by placing and manipulating keyframes in the timeline, but you can also record a manual mix session using the Auto section of the Audio Mixer. This will let you ride the levels and record whatever you do (basically generating a whole bunch of keyframes).
They are not necessarily two paths to the same goal. They are more like any typical audio mixer, where you will have an input gain knob per channel as well as a channel fader. You just happen to now have both of these on any clip or segment. Changing very hot music files is typically something you’d do with Clip Gain. Making an actual mix is more what you would do using AutoGain/Volume. But different folks use different methods, of course.
Also realize the order in which sound is routed in MC. Any clip will go FIRST into Clip Gain, then into AudioSuite, then into EQ, then into the track’s RTAS, then into Automation Gain, then into the Master bus.
It is important to realize, because for instance if you have a clip in your timeline and you have an audio compressor on it, raising the Clip Gain will raise the INPUT signal to the compressor (thereby raising the amount of compression), while using AutoGain will raise the OUTPUT signal of the already compressed signal (not increasing compression amount at all, but raising output levels). In cases where you would use a brickwall limiter, you can easily tell why it would be important to know which happens first, because using AutoGain would then let you raise levels beyond that brickwall.