OK, SPI is looking pretty good; actual bit times are identical to what-they-should-be, so I'm not even going to note them down (whereas UART out of the PI has some drift, probably strange BAUD fractional maths).
So, there's just the question of waveform integrity, and (probably) the ability of the RP2040 to keep up, and there's the actually-delineating-and-echoing-etc test.
I'd like to look at some scope traces first, but I should probably do it in context (i.e. actually driving a pin, not free air), so I'll setup my little test rig...