I have flow a number of the "VLJ's" and larger corporate jets.
They are a pleasure to fly... they really do just fly like a big 172 however you can get yourself into more trouble quicker.
DO A TYPE RATING IN THE SIMULATOR - This is the number one rule, and it wouldn't hurt to do a recurrent or two.
As it has been noted there are a few performance issues like runways, climb gradients and hot and high performance that you may want to take a course on while you are in the USA doing your type rating. Flight Safety and CAE run all sorts of add on courses that will help.
As for the single pilot thing, it is not such a big deal. The aircraft are designed around this with electronic check lists, fadec engines and simple systems (Fuel, Hyd, Pressurisation ext).
They biggest problem is when people start trying to use them for what they were not designed to do. A Mustang for example is a great Sydney - Gold Coast aeroplane with the Wife/Kids or Mistress/Golf Clubs, not a Melbourne - Perth (With a couple of fuel stops) with 5 passengers for a business trip.
For someone with little or no experience I would suggest you may want to spend some time with someone who can show you the ropes after you have done your type rating, it is important that the person you choose isn't your mate who is now flying for an airline (no offence guys) but someone who is operating these types of aircraft all the time, then you can fly with your mate who probably has some great advice to add to your knowledge. Also it may pay to get some advice about Maintenance and programs available as it is a little bit different to the normal GA type of stuff. You may also want to get some advice on RVSM, PBN and ADSB approvals and what not (I am more than happy to give advice in this matter in exchange for beer).
If you are flying around in your Kingair, Conquest, C421, Navajo or any other high performance twin the conversion is a lot easier than you think. My advice is to go an buy one...