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You can go two ways. The more expensive would be a specially designed padding that can be cut to the dimensions of the desk top. It has some grab to it so it doesn't move a lot.
If you go glass, you will have to go to a glass store. You can get larger sheets of glass cut at your hardware store, but that is window quality, not thick enough for what you need, and the edges won't be "honed" down in order to avoid cuts and believe me, you will get cuts with this type of glass, some can be serious.
A specialty store can take your dimensions, give you a thicker glass perhaps tempered, and grind down the edges as long as you explain what you are going to do with it.
Finally, you say you are going to paint the desktop. If you lay glass over it, make sure you get some of those little green circular felt protectors to place under the glass. Otherwise, you are going to have paint sticking to the glass at some point, pulling it away from the desktop. The only way I know of to avoid that is using a hard drying expoxy based paint, that is allowed to dry completely and the desk not left in a humid situation.
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