I'm not 100% on the painting chrome thing but paint does need a rough (ish) surface to actually grip to, so I'm pretty sure that you would have to do something to the chrome first... At least.
In regards to the exhaust, my guess is that fitting a smaller bore, if you're talking about the pipe through the middle, would strangle the engine a bit. Obviously depending on how much smaller you go.
they are two separate questions.
you need to sand the chrome to rough it up
and any aftermarket muffler will flow more than the stock so diameter isnt as important as you would thing going smaller. it may look weird though
The chrome bit that you want to paint, is it a part of the exhaust? Or summat else? i.e. - something that won't get as hot. Either way, you'll need to rough up the surface quite a bit and if it IS on the 'zorst then use a heat-resistant paint. But if it's going on a header pipe then it still might come off.
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