Michael - that's pretty much what I was thinking. But, I would disagree with part of your method - to do it in the slicer. I think your method would best be done in the original modeling program.
But, HONESTLY - I bet there HAS to be a way to do it Purely by Slicer - like assign 1st outer layer of object to 1 material, and the rest to another material.
NOW - I will go a STEP Farther. In fact, I've done a GOOD Bit of work directly modifying GCode. I bet one could actually create a post processor that could Mod the GCode - and force the outer layer (or Loops at the OP stated) - to use a different filament.
No - it's not THAT simple of a task - but, it COULD be as simple as a Tool Change command insertion!!!
If I wasn't DEEP in the middle of a Move right now - I would dig into this idea myself...
Just now - I even thought this might be a cool little problem to throw at Claude AI - since I am already using it in a BIG way for Coding assistance!
Anyway - we still need some feedback from the OP - as he didn't answer several questions - and now he needs to respond to several of our replies!!!
-K