If you can make good progress and keep your day job and benefits, that's always a good thing. If you have spouse/kids that can be hard, but if you're single you can make a good go of it.
A current employee will usually have better odds than an ex-employee. An ex-employee with a good record will have better odds than someone off the street.
Most people break into corporate based on who they know...you have to hang out at the right kind of airport and network. You generally start out doing occasional pay-per-day freelance gigs to cover for the regular pilot who is unavailable. In some cases the boss only employs one pilot full-time and then free-lances the right seat for every mission. You generally will need to buy a type in a citation, or start in something which doesn't require a type. You'll probably need 1000 turbine hours and a type before you can start getting into the decent jobs.