I am creating a product prototype that will require finishing.

Which material is best for sanding smooth and then priming/painting over?

If possible to go into detail. Which one is easier to sand? Which one Sands smoother? If I am already sanding, is it worth printing at higher resolution? (100/200/300 micron)

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I would say as far as sanding goes, PLA would be the easiest to sand, and ABS the hardest due to PLA being a relatively soft material. However, you can use acetone to smooth ABS parts very easily, minimizing the amount of sanding that needs to be done. Printing at a higher resolutions would lower the amount of sanding that needs to be done, but raises the print time. If it were me, I would print with ABS at 200 microns, and use sand paper to smooth initially, and then acetone to get a glassy finish before priming and painting.