I'm not a pro, but do the photography for an oil painter friend. We just take the paintings outside in the shade and do custom white balance. But with bad weather settling in, later this week we're going to try shooting indoors using one flash and a shoot-through umbrella. I don't have high hopes for that, but I think with two flashes it should work pretty well.
So I'm looking forward to hear what the pros here have to say about the lighting. The big enemy would be reflective glare, followed closely by uneven lighting on a large artwork. I just don't know if those who specialize in this niche use any particular lighting - such as really broad spectrum lamps.
I would think the 100mm lens at its sweet spot aperture on the 5D would be great, or the 50mm if you can't back up that far. Not the zoom. Just be sure you position the camera square to the picture and directly opposite the center of the picture, and you have it and the artwork level. That will make life easy when you crop. Use the self-timer or a cable release to avoid any shake.
Somewhere I saw a suggestion for getting the camera at the right place, and that was some kind of rig that placed a mirror at the center of the artwork. Then you move the camera until you see yourself in the mirror when looking through the viewfinder.
You will find that you can make the photo look better than the painting, and your artists may like that, but it's not a good idea. You don't want a collector to be disappointed on seeing the painting live. So resist making it pop more than the original does.