You might have a leak from one of the valve covers and it is dripping down on the hot exhaust manifold. Some 92 LT1 motors had problems with leaks from the front cover or front seal but that would show as drips on the ground.
As far as temps, they sound about right (oil is fine) but if the coolant temp is constant at 210, that is a bit too high. My 92 will run between 197 and 205 most of the time. On really hot days when I'm stuck in traffic, the temps will seldom go above 220 but when it does, the secondary fan turns on and the temps drop rapidly. Turning on the A/C automatically turns on the second fan and it remains on as long as the A/C is running. You should check the front of the radiator for debris. This is pretty common on C4's and you will be suprised to see what sort of junk can collect there. Use a garden hose to flush out the junk by directing a stream of water from the back side of the radiator and pushing the junk out forward. Also check the front of the A/C condensor for any debris.
14.4 volts at start-up is about right. I would check the overall condition of the system anyway. The factory battery in my 92 vert lasted 11 years and it never really died; I just replaced it as a maintenance item before I drove across country for the 50th Anniversary Caravan to Bowling Green last year.
It would be a good idea to have the cooling system flushed and a new 50-50 mix of coolant (green) and distilled water installed. You could go to a 180 degree thermostat to help with the temps a bit. Also have the tranny serviced at a reputable shop and have the fluid flushed and a new filter installed. You should also have the brake fluid flushed and use a good DOT3 or DOT4 fluid. Change the differential fluid and add a bottle of the GM posi additive. BTW, you did use Mobil-1 for the oil change, right?? The factory requires a synthetic oil to be used and 5W-30 Mobil-1 was the factory fill.
DO NOT use a pressure washer to clean the motor!! The Opti-Spark distributor, located directly below the water pump does not like water and will fail if it gets wet. This is a costly part and can run upwards of $500-600 to have replaced :eek I use a 50-50 mix of Simple Green and water and some old brushes and rags to clean the grease off. Non-chlorinated brake parts cleaner in the big spray cans work well too.