In OR3:
You can select the mesh and apply the material?
You can select the mesh coplanar? "obj with single material"
Here I exploded srf and created two different materials to be imported in octane.
Thanks!

Octane is still and only a render engine, it is faster and lighter also because it doesn't has all the unnecessary stuff that you can find in any modelling app.
Before starting octane I have decided everything....Having said that, if the material is already available, you just need to assign the material to the new face in your host app and reload the mesh with the proper button in the node inspector:
I do dozens of unnecessary things and hope not to have committed mistake? .... Is this a correct workflow, do you think?In the past, when there was the standalone only, my strategy was to export extra materials assigned to hidden cubes (in general under the ground or in places not visible from the camera). In this way you have more flexibility if you have to change the scene later on