You confuse me:
„between the LED display (using an STM32F103 64-pin, to drive an array of LED's) and the main MCU (STM32F103 100-pin)“
„I don't think the UART connection has any role in controlling the LED display, because it doesn't actually connect to the primary 100p STM32F MCU.“

There's actually multiple communication lines going to that LED display PCB, which is kinda hard to see in the image, but are labelled in red, on the 10pin connector.
- 2x pins for UART (Tx/Rx); those are the pads that I showed in the previous image with a green arrow. While they do go to the 10pin connector, there are unpopulated resistors on the main MCU board, therefore, do not have any role in communication with the main MCU
- SDA + SCL for the temp/humidity sensor
- 2x pins (which are the ones
in regards to this post), which I'm assuming at UART TX/RX, but I'm not 100% sure, hence this whole post. I guess I could hook up my scope to *both* of these pins and see whether there's data on both pins, or just one?
Then there's 2x pins for 3.3v/ground, one pin which connects to "NRST" (Pin 7) of the 64-pin STM32 MCU, and then a final pin which connects to an unknown I.C on the board.
I‘d say it depends on the implementation or the used framework or simply the efficiency whether it is plain text or pure bitstream.
How can I determine whether it's plain text or "pure bitstream" (whatever this means?). I'd assume there's probably a YouTube video on this, or maybe a post on the EEVBlog? I'm just not 100% sure what I'd need to search up.
I work in automotive electronics development and have to deal with communication from high level down to bit shoving.
You measured the bit duration several times, eg 5th screen shot, I did the math 1/115200
To decode the protocol you would need to analyze which packet causes which reaction on the display.
I wish you a lot of fun doing so and keep asking if it’s really worth it.
Is decoding the protocol + packet analyzation something that is generally difficult to do? Would I be able to use an ESP32/Arduino to simply send an identical packet (as I recorded with my oscilloscope) to see what happens?
Additionally on my Siglent oscilloscope, it gives the options for me to specify "Data length" (values between 5-8), "Parity check" (none, odd, even, mark, space), "Stop bit" (1, 1.5, 2), "Idle level" (low, high), and "Bit Order" (LSB, MSB). I have no idea what any of these are, but are they easy to determine based on the images I have provided. Further, will knowing these aspects of UART be required if I were to send data with an ESP32/Arduino?