Does size really matter?

I mean the scale of the scene in Maya when rendering with V-Ray?

Will an object that is 100 cm, look different when scaled up to say 10000 cm?

It will depend on the scene, but in most cases the output will look differently. The size effects almost everything in the scene: the lighting, materials set-up, camera settings and so on.
Therefore we recommend working in real size.

So as long as everything is in a real scale (whether the scene is 10m in size or 6km in size), it shouldn’t affect the look?

I ask, because I have a scene that is 20km across and I have to add in some pretty high values on things for them to work.

Some things in V-Ray do depend on the scene units, specifically the physical camera parameters, lights that have photometric units, and IES lights.

Best regards,
Vlado