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My wife has an interest in trying out my miniwargaming hobby, but is overwhelmed by the scale and complexity of 40k. She does however like X-Wing. I was thinking about grabbing the set as a way to get some models, dice and terrain for us to play with. Also, since I know Infinity can get complex, we could use the scenario book included and just pause at whatever level she feels comfortable at.

Would it be s good buy for those reasons?

This would be very good for those reasons, but yes, it will likely be too complex for her liking beyond the basic starter missions. I always like to suggest Pulp Alley for situations like this. It's a bit more narrative based without really being an RPG (or even an RPG-light). It's a bit on the simpler side for mechanics but with a fair amount of choices in-game, and has a really good character creation system. It's designed around 1930's pulp action, but works fantastic with no modifications at all for everything from Great War and WW2 through modern and sci-fi.

But yes, it's hard to beat the models you get from OI, they're fantastic. Additional Moto.tronica packs will help you build a table worth of terrain real fast, add in some die-cast cars and you have a neat start for Infinity and Pulp Alley or any other game you want to use the rules for

It is for those reasons - provided you like the aesthetics of those two starter sets included (miniatures).

If you liked any of the other faction's models, then no it really isn't.
As two starters for other armies and a set of the mototronica scenery (the scenery included in the box) are available separately anyway.

Would sectorial starter armies be good expansions for Operation Icestorm? I'm looking at "Neoterran Capitaline Army" and "Corregidor Jurisdictional Command".

I wouldn't recommend it. The generic starters that make Icestorm are solid foundation. I'd advise to expend it with few individual purchases.

As someone who was really interested in getting into Infinity but a little daunted by the rules, I think O:I is a fantastic starter set. The missions are really well thought out to introduce you to the rules [first one is just a 3 on 3 kill mission] with slowly increasing complexity. I've played through the missions a few times now [you could probably do all of the missions, swapping sides each time, in an evening] and now feel ready to start taking on the full rules. I'm totally hooked and have now bought about 400 points of Haqqislam and sold off the majority of my 40k stuff - this really will hammer home how poor the 40k ruleset is!

Very impressed with the scenery kit included as well which makes it an absolute doddle to transport around. In terms of the miniatures, they seem to be really good starting points for an army. There is a page with suggested additions to take the points up to 300, and there are bundles for both factions to get the models to match. If you want to go another way it's really easy to add stuff - I've also got nearly 300 points of Nomads with O:I plus the Corregidor Jurisdictional Command starter. If you've no interest in playing either Pan-O or Nomads they are still lovely sculpts, or just Ebay them.

The only thing I hate about the O:IS are the mission victory conditions. They all lay out this increasing complex system of points you earn for killing the enemy models and having your own survive, but then the game end conditions are always tabling your opponent, and the only missions where it's possible for the person who got tabled to win is the last one, and only in a very specific way, so it's really just a pointless addition and kind of bugs me with its general irrelevancy.