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In LW each weapon has very distinct uses and it tells you so in their description and some loading hints.
In vanilla there is little difference early on and you should not be struggling in that way with the air war.
Anyway, the diffrence between the two, for the OP, is that the stingray missiles do more against armored UFOs and avalanche missiles are better for non-armored ufos. You should generally safe stingray interceptors for taking down raiders if they stop by, and avalanche for the scouts and stuff. The air game in Long War in my opinion is a bit unbalanced with the repair times and power of ufos, so there isn't really much that can be done with 2-3 being needed to take down a scout. However for the raider problem having one with stingray missiles, while it still won't do so well, at least should give a chance.
Stingrays have better armor penetration, so use them against fighters (The only small aircraft with armor).
As for aim, aggressive gives you the highest chance to hit (55% base on starting weapons) so always do that. The enemy ufos already have more aim than your jets so u need to get hits in when u can.
Most importantly, every kill a pilot has increases his aim by 3% and his damage by 1%, up to a max of 30% and 10% respectively. Keep that in mind when choosing pilots to go on important fights.
Unfortunately, I am chronically short of alloys, due to having a ton of item repairs, so it will be a while before I can manufacture a third such laser.