How does the WAR suit ability Shield Wall work

• The attack is only triggered by enemy movement. Moving on your turn will not trigger Bladestorm (unless your move causes an enemy to move, such as a burrowing Chryssalid).
• No, only the movement will trigger Bladestorm. I've had an Andremedon move past my soldier (triggering Bladestorm), then in a separate action, make a melee attack. The attack was not responded to by my Ranger.
• They happen immediately, usually before the enemy gets to take their action. This is very useful against, e.g. Stun Lancers, which will move into attack range but die before they can actually make an attack. Some enemies, such as Faceless, have a melee range larger than the Ranger's, and don't actually have to move close enough to trigger Bladestorm to attack. (It seems there may have been a recent patch affecting this; it's possible for Bladestorm not to trigger until after the enemy gets to attack.)

Since no one (other than Firaxis) can know for sure, here's my interpretation of your picture:

The soldier you're trying to target isn't standing in the open door, but next to it. He's standing in the same line as your soldier, and the full-cover-box you can see behind the doorway.

I think it's that specific box that is blocking your LOS. Even if we consider that your soldier sidesteps (so let's assume she's standing one tile to her left); it's possible that the slight elevation of the train cart combined with the angle of the box (relative to how your unit would see the enemy soldier) leads the game to decide it's not in LOS.

That being said, this is just a guess. I remember being in similar situation and seeing my target. The only thing different here is that box, which is why I'm thinking that's the reason.

Edit
For those who argue that the enemy (model) is in sight of the soldier, therefore it should be targetable, keep in mind that the game calculates based on the tile a unit is on, not the actual visibility of their character model.

I find that units in cover really cling to the cover, or try to pop out their heads, and it throws off your vision on where the tile is located. If you look at OP's picture, you'll see how much difference there is between the enemy's body and the actual center of the tile they're standing on.