Corporate jobs are like rocking horse manure!!!
Get licensed first , many charter organisations also have a flying school so the school inevitably is a good source of co pilot material. The instructors are more often than not supervised by their CFI who guess what.... is inevitably cheif pilot of the AOC charter operation.
The chance of getting straight into the RHS of the aircraft you describe after finishing your training is very slim, however some citations can operate single pilot and if you come across a freindly corporate pilot (very common - nice chaps generally) you might just get a RHS trip on an informal basis.
I got into a corporate job in exactly this way....
Some general pointers:
1. Try and endear yourself to a potential captain on the ground, in a lot of cases you will be spending 6 hours a day sat 12 inches from shoulder to shoulder, you will also need to use your wit & repartee to keep said captain very entertained on Nite stops. You miht be chuck yeager but if you are a total muppet your grounded!!!!!
2. Appearance is everything - somebody doesnt fork out 5mill $ to have a scruffy urchin sat in the front of it. I would say more so in the corporate job than an airline or instructors job your appearance is paramount. Polished shoes & newly pressed pants are a must on every trip.
3. Inevitably most corporate aircraft are on the US or less so recently the cayman Islands register. If you are going to do some hourbuilding do it in the USA and get a FAA PPL with a twin rating as a minimum.
Good luck with your training but dont hold your breath. Corporate jobs are just as rare as airline jobs. Once into the job though its brilliant, fantastic challenges every single flying day.