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So i'm sorta mixed on the issue. Many used to say large creatures were best for poisoned weapons however regardless of what it is it wounds on a 4+. Considering armor and other such ridiculous saves this generally leads me to the conclusion you don't want it for infantry, monstrous or gargantuan creatures but rather bikeers esp. given they can jink and get a cover save even if you would take down their armor save. It also may be good against ogryn sized or tough units like wraithguard, ogryns, grotesques and other types (what's the toughness on thunderwolf cavalry?).

In some cases i'm unsure since unless bikers jink blasters are the preferred option. Also blasters do instant death whereas most poisoned doesn't and blasters can threaten super light vehicles and monsters somewhat should the need arise.

Comparing a blaster to a splinter weapon is like comparing a plasma gun to a bolter. Of course the plasma performs better but the cost is exorbitant.

The most used splinter weapon, the double venom cannon, reliably puts 4 save on anything not gmc on the table. The best US is where you see those wounds effecting the most. You need 3 venoms to do 2 wounds to a riptide, while they do 4 wounds to a 3+ save. 12 wounds to 5+ saves. So poison is about Mathing out expectations then getting happy when th opponent fails more then expected.

they're ap5 weapons so lightly armored, high toughness targets are the best things to shoot at. Tragically it is unlikely you will see many of them on the table.

in bulk they do work, but don't expect them to be more than what they are.

Targets that I like to shoot at:

-Riptides, because they do still get past that 2+ and every bit helps
-deamons, generally they have their deamon save so it doesn't matter what you shoot them with. bulk poison does fun things to demon princes
-nids, High toughness, low armor saves. Downside is that you'll never see them on the field.

When picking units to use poison, look at the point cost per poison shot. poison is good in bulk, so you need lots and lots of shots.

Idea targets are high cost but bad armor units. Sadly, not many of those, so your general choices are between expensive units with good saves and cheap units with bad saves. It all depends on how the game is going at that point for what you target.

Dual cannon venoms are just good at forcing armor saves, so keep that in mind.