Let's write out what you are computing. Suppose your data is $$\{S_i,V_i\}_{i=1}^{i=50}$$ Of course $P_i=\frac {S_i}{V_i}$
What are your two procedures? Assuming I have understood you correctly we have:
Method I: $$\frac {1}{50}\sum_{i=1}^{50}\frac {S_i}{V_i}$$
Metod II: $$\frac {\sum_{i=1}^{50} S_i}{\sum_{i=1}^{50} V_i}$$
Phrased this way, it's clear that they are not equal in general, no?
The big difference, to me, is that method II is dominated by the big volume days whereas method I is not. As an example, suppose you only had two observations: $$\{1,1\}\;and\;\{2^*10^6,10^6\}$$ The price for the first day is $1$ and for the second day it is $2$, hence Method #1 gives $\frac 32$. But method #2 gives:$$\frac {2,000,001}{1,000,001}\sim 2$$. As I say, the low volume days simply don't register.
Conceptually: The first method gets you an average Price (it literally computes the average of the price realized on each day). The second method gets you "the average realized value of a unit of your product". These will be comparable if the volumes from day to day are roughly constant, but not otherwise.