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smell it. If it smells of coolant, you have a problem.
You live in a part of the country that can get muggy, but if your the least bit cold, the humidity will drop off.
It COULD be the cats, but I doubt it... there is a chance for a bad headgasket, bad cleaning of the block causing a small leak, something silly stupid annoying like that.
No, a bad cat won't necessarily cause smoke, but a good one will - it's normal at start up depending on temp, relative humidity. In fact, must mufflers have weep holes at the rear to help get the water out, particularly on the Vette, where there's an uphill climb to the muffler.
Worn valve guides. A little oil drips past the valve guides when the engine sits a while. As long as the oil consumption isn't too much (like maybe a quart every month or two), then it really isn't a problem. In fact, a little lubrication just before startup is a bit helpful. But do track your oil usage to make sure it isn't something more serious.
If the smoke is blue, it's oil; if the smoke is white, it's water vapor (black is fuel). White smoke can be from the water produced during combustion and is normal - it should not smell like coolant. If it does, there's an internal leak (gaskets, cracks). Typically on an OHV engine, a little blue smoke on startup is from leaking valve seals. Worn guides should produce smoke while running as well as at startup. The valve seals should have been replaced when you did the p&p, but it's possible to dislodge the o-ring seal from its groove when installing valve springs if you're not careful. If you had the guides knurled or grooved, they'll leak forever!