I used the Suvarnabhumi Airport to udon service a month ago; you just use the free airport shuttle service to the transportation centre and walk down to the ticket office, buy your ticket and the bus stand is only 30 metres away, by the entrance to 108 shop (like 7-11). Bus is mustard yellow in colour and fairly new, has 825 in service number and says destination Nong Khai (and Udon i think). time: 8pm and 9 pm. not certain about daytime services, but these times fit in with many planes which arrive around 6-7pm. you get blanket, water, snack and maybe milk. Driving standard good, bus usually half full or less, can get some sleep (i take inflatable travel pillow). Only problem: 9pm service arrives in Udon at about 5:15am, not much open then. Cost 418 baht.
Return service a bit more problematic: english signs few and far between at Udon central bus station. But buy your ticket at one of the offices to one side of the bus station (south side, office nearest main road). Only one service i think, at 8:30 pm; leaves from stand 5. The yellow colour and sign on front saying 'Suvarnabhumi' will tell you that you have the right one (also 825 service). Arrives at Suvarnabhumi transportation centre around 4:45 am; shuttle services start at 5:00am i think. This means fits in with most early morning flights with some time to spare.
I am told there are no VIP coaches running this route. But anyway service is quite good and will use again.