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Both cause the "same" poison status buildup.
If you apply both the one which price will be the damage going out.
Your best bet would be, as you mentioned, DP and Rot, or DP and frost.
Getting frost procs is really nice with DP
https://youtu.be/wSfPcorlwTM
You probably know it already, but i suggest using a rot status effect, they should stack, i think. Or bleed. Or all three.
There're also madness and death status effects, those are pvp focused pretty much.
Different levels of poison (which I don't believe there to be any) would not stack, as they're the same effect
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You really don't need Poison Moth Flight if you are looking to apply Deadly Poison since it lasts only 30 seconds. If you use the Kindred of Rot talisman with your Serpentbone Blade, you get 20 seconds of increased damage whenever poison is applied. This means you only have to wait 10 more seconds before you can start reapplying poison and receiving the damage buff all over again.
Poison Moth Flight is better with regular poison, where it does less DPS but last 90 seconds. Waiting 70 seconds is not worth it if you are looking to rebuff your damage, so PMF does a lot better here.