My biomedical engineering thesis was entirely coded on octave, and I still use it daily even though my current employment does not directly relate to it code-wise.
Also, while perhaps this example is overplayed, Andrew Ng's hugely successful coursera nanodegree on Machine Learning is taught on octave. Andrew Ng explains the reasons for this beautifully in his course, and I agree.
As for "I thought it would be a valuable skill; I could not have been more wrong", it depends. To remove the obvious comment, there is octave, matlab, and octave/matlab. Matlab is still 100% huge in the industry, and getting into this path through octave is at least equivalent, if not better (given you also have to learn more under-the-hood concepts than you might have to in matlab).
However, I will assume here that you are referring specifically to the whole "investing in the octave ecosystem on top of already knowing the matlab language" issue. I would argue that octave tends to be more used in teaching and academia, so you're partly right. But at the same time, I would argue that as an open source project, the opportunities for participation and the transferable skills you can get from that are extremely relevant in any resume.