As posted I would talk to the Air Guard about getting a pilot training slot(Officer position) right off the bat. Yes, it may be down the road a bit, depending where you are in college.
To the other question, yes, one is in a better position applying for a pilot slot if already an enlisted Guard member. Some steps may require faith at times, ‘no guts, no glory’.
Even if one is setting themselves up for an airline job, in most instances I’d reccomend military flying if it’s an option for the individual. It’s not for everyone. A Guard or Reserve flying slot would hardly hinder(only help) a track towards an airline job. It would just require a bit of juggling.
Of course when one dabbles with the idea of the military, be ready for the ‘commitment’ part of the deal.