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Essentially, whenever you inflict poison on a target, it's stored as a concrete amount of damage. Once the enemy's poison resistance threshold has been crossed, all of the poison damage you've built on the target will start ticking down over a period of time.
Now, here's where S&S differs from other games. Once the damage starts ticking down, any further poison damage you do to that target will *immediately* apply to the enemy and start ticking down along with the previously delivered poison damage, basically increasing the poison's rate and duration. Just because the foe's poisoned doesn't mean the poison can't get more severe.
Now, as for bosses with 500 or more poison resist, due to the way defenses work that means your poison buildup AND poison rate will be reduced by a little over two thirds. There aren't really any enemies that are actually immune to poison, but with resistances like that it's usually way more of a pain than it's worth to try and stack up poison on the boss; frequently you'll find the poison tapering off WHILE you're still building it up.
There are unfortunately quite a few bosses who are extremely resistant to poison, but those that aren't tend to wither and die alarmingly fast once you've built up enough poison on them.
The mireheart charm is some heavy duty stuff, so you might want to consider using the vile charm from a secret area near the start of the Red Hall to bolster your poison output instead if you don't feel like constantly chugging antidotes in the middle of a boss fight.
Also poison scales exclusively off of dexterity even if an innately poisonous weapon says it scales off more than just dex, and multiple sources of poison damage do indeed stack, so a virulent scimitar with pessmud and a vile or mireheart charm would poison faster and more intensely than just a virulent scimitar.
In answer, poison can work just fine in NG+, but only on the right foes. Resistances don't change between new game cycles, just HP.
Does the damage from spell poison gas also scales off of dex ?
Wow thanks for all the information.
While I'm at it, Pessmud and Mossy Pessmud, like any other item-based buff, scale off of your weapon upgrade level as well as the weapon's total attack rating.