Honestly, OTP isn't much different than writing for any other chip, the difference is just you only get one shot per chip. So if you made a mistake in your code and burn a chip, oops it is trash so you start over with a new one. Also, I kinda use machine and assembly language interchangeably, but in reality they do have some slight differences with assembly technically being slightly higher level than machine, just be aware some purists get on their rants about this, and literature can sometimes be confusing if you don't know there are a few differences.
You'll have to pick up their machine instructions and learn them, since it is RISC based they likely stuck close to one of the RISC based standards as there is no reason to reinvent the wheel. You can absolutely do it, I would just think it might make more sense to start just a little higher level first, then go here. But I totally respect jumping to the lowest level and working up as I have done that too.
To get started, I am sure they manufacture a programing/flash board, buy it and a bunch of chips. Find a problem to solve that makes sense given what you are working with, and learn their machine instructions. If you know how to program the basics are the same, except you have to manage everything, clock, RAM, register spaces etc. Lots of good books on embedded work, just remember that the chip you are looking at isn't really a micro processor, it is a limited micro controller.
I started off in Basic, C, Pascal and Motorola assembly (then x86) way back when, then kinda settled into C/C++ for low level and Javascript for pretty much everything else, except mobile. So how I learn these is just by doing exactly what I am suggesting to you, find a problem that seems fun to solve and just start working at it. Sometimes for my own sanity, I would write things in C to get a feel for what I wanted to do (just mocking up in/outputs), just helped me think a little higher level at first. I would also many times output the assembly using gcc as a way to give me some ideas, but usually that is just an idea since these small micro controllers aren't likely supported by any major compiler.
Good luck, this can be a ton of fun.