first time multiplexing/charlieplexing for a complete beginner

Lighting single LEDs works flawless. Now I just need to find out how to put some more "action" into the whole thing.

A 2x3 matrix would require 5 pins from your controller, multiplexing is only saving you 1 pin over controlling the anodes or cathodes independently, so its realistically only practical as an learning example.

That's true, i've done it that way because an ATTINY85 has only 5 I/O pins. And yes, it is also for learning :).