The new RP 2350 has an enhanced PIO that relaxes some of the constraints the author ran into here.
Also the new HSTX (high-speed serial transmit) unit is really well suited for rapid line coding.
Here's a different project that generates a high resolution high depth VGA signal from the RP 2350: https://www.breatharian.eu/hw/disphstx/index_en.html
And here's NTSC composite using just the original PIO: https://github.com/obstruse/pico-composite8
The issue was not with PIO. It was with the fact that both rp2040 and rp2350 only support usb1.1, which doesn't have enough bandwidth to do uncompressed ~320x240x16bpp@60Hz.