You can round the edges nicely with a round over bit the same you do MDF etc.
I generally use a cheap 3.2mm roundover bit for 3mm acrylic.
It polishes up very easily to a high gloss shine too.
I start with 320 grit emery/wet n dry and polish it until the machining marks are removed. You can then go up the grades one by one to get it nice and smooth. I tend to go 320>600>800>1200.
Once you are there the edge should look translucent and you can then apply Novus 3 with a cloth followed by Novus 2. You should be left with a crystal clear (for clear acrylic) high gloss finish.
I did this dreamcast CP top for a customer a couple of weeks ago, you can just about see that the edge has a polished, radiused edge:
