At your age, a regional career is feasible, or you could do regional for a couple years, get the turbine time, then go corporate. If you were to pursue a major airline career, you would be so old by the time you got there that the dues / payoff ratio would be very high..ie you'd spend most of your major airline "career" on reserve in some east-coast toilet.
IIR, the 141 program will require that you do the ENTIRE comm & IR syllabus...since you already have 185 hours, look at doing the IR part 61...by the time you do that, and do the comm x-countries and manuevers, you should be around 250, so you could take your commercial ride part 61 also. Just run the numbers both ways...don't get fixated on using your VA benefits unless they will provide some significant savings. Many 141 schools make sure they overcharge VA students so they can get your benefits...compare the 141/VA cost to the same rating done under part 61.
The one big potential opportunity for VA benies is a 141 program where you do most of your training in a twin and get your 100+ ME knocked out...there are schools that do that sort of thing.
You didn't say anything about CFI, CFII, MEI...assume that you will need those, even though some salesmen will probably try to tell you otherwise. Flight training salesmen are usually people who got booted out of the used-car sales union for ethics violations...
You mentioned "going the distance to ATP"...not sure if you were talking about the school ATP or the ATP rating. If you were refering to buying an actual ATP rating...that is almost never done and would be totally unnecessary...get your CFI ratings, get a job as a flight instructor, then when you have 1000/100 go to a regional...they will automatically give you the ATP when you upgrade to captain.
If you're gonna do it, get started quick.