I wonder if you're being a bit quick on the key - turning it on, but then letting it turn back... I have noticed with my Defender 4.0 (which I use as my bell weather as I've had it almost from 5 yrs old, it has always been properly serviced and has almost undetectable HC in emissions testing) that if I am a bit quick to release the key ie before the engine's caught then I also have issue on the second turn - assuming same as you, over-fueling.
On the RR 4.6, it is generally well behaved, but in this weather it has missed the odd first-turn - and I haven't yet eliminated that being my poor key-turning etiquette (ie being too accustomed to the instant catch, but being too impatient to wait an extra couple of secs). It hasn't stressed me enough to get the nano out and start looking at temps yet, but I may do out of idle curiosity. I was looking at trims the other day though, and noticed the ECM uses the same 38.75% at start up that it was using in the winter, before the o2 sensors kick in - now, if I can only work out how the ECM determines that start-up value I could maybe fool it. Has anyone decoded the mysteries of the GEMS fuelling tables ? It had a new ECT last year, I can check it, but I doubt it's that.
On the RR, my IAT has an extra resistor across it which gives me an extra 10-15 degree boost, but typically still a few degrees below ambient. I did even have the IAT disconnected for a while (by accident) and although connecting it again it seemed to make starting a bit better, it was not dramatic. Which is all to confirm that the IAT prob doesn't have too much influence, as Rave implies
50th RR 1998 4.6L GEMS, 50th Defender 4.0L GEMS, Nanocom Evo (P38/ GEMS)
Formerly 200Tdi 90 CSW and SWB Series 3
SW London