Below some math to compare the two. Note that the math is slightly flawed as resistance is a lot more complex than portrayed below. Some assumptions such as the average armor were made. In addition, some other factors influence the total outcome that are not listed below. Regardless, it gives an idea of the situation.
Lil Timmy's Peashooter
10.96+4.5 Bullets = 15.46 raw DPS
25% average damage reduction from armor
15.46*0.75 = 11.60
Venomstrike
9.58 DPS+3.5 Arrows = 13.08 raw DPS
25% average damage reduction from armor
13.08*0.75= 9.81
Proc
Proc rate = 10% (source = classic wowhead comments)
PPM = 60/10/2.4= 2.5 PPM
2.5*38 (avg proc dmg) = 95 DMG
~7.5% average resistance = 95*0.925 = 87.875
87.875/60 = 1.46 DPS
9.81+1.46 = 11.27 DPS
Instants
Arcane Shot and Serpent Sting favour Venomstrike, Multi-Shot is more complex.
If you get one extra proc out of Venomstrike from instants per minute you will outperform Timmy's.
This means you need to use 10 instants or more per minute, aka once every 6 seconds.
This seems very doable, desireable and likely, ultimately making Venomstrike better.
Conclusion:
Venomstrike is generally better.
- Especially vs classes with high armor and low nature resistance.
- The advantage of Venomstrike gets bigger the more instants you use.
- Vs low armor classes Timmy's might be preferable.
- Rogues/Warriors don't use ranged instants. I'd recommend Outrider's Bow + Feathered Arrows for those two classes as they need much fewer ammo for max DPS. For single shots, use Throwing Knifes.
Should I've made any mistakes, please point them out so I may make amends.