Rough up the old one with a fine grit sandpaper or steel wool. That will help the new paint adhere. I would not be afraid to spray paint a toilet seat, but I would not use any kind of paint other than enamel. Anything with latex will simply peel off as you use it. Could be annoying.
If you do spray with enamel, do so in well ventilated space, make sure anything you don't want overspray to get onto is covered. LET IT DRY very well. Most enamels factory done are baked on to create a very hard and durable surface. Spray painting at home cannot duplicate that process.
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