Question 1. Are the states $s'$ drawn from a from a joint probability distribution $P_{sa}$? In other words, if you are in an
initial state $s$, take an action $\pi(s)$, then $s'$ is the random
state you would end up in according to the probability distribution
$P_{sa}$?
This is tricky, because you don't show a definition of $P_{sa}$. My first thought was that you meant the transition matrix $P_{ss'}^a$, but that doesn't fit with the phrase joint probability distribution.
If you really mean joint probability distribution then the answer is generally "no", because $P_{sa}$ should be the probability of observing state $s$ and action $a$ when taking a random sampled time step:
$$P_{sa} = \pi(a|s)\rho_{\pi}(s)$$
where $\rho_{\pi}(s)$ is the distribution of states under policy $\pi$. Note this makes no reference to $s'$ at all.
However, there are ways that this could relate to the distribution of $s'$. Probably the most direct relationship would be when there is a deterministic environment, thus knowing $s$ and $a$ would determine $s'$. If, in addition to that, each $s'$ could only be reached from a single $(s,a)$ combination, then knowing $P_{sa}$ would also give you knowledge of $P_{s'}$ - this is not the same thing as the question is asking though.
If you did mean the transition matrix $P_{ss'}^a$ instead in the question, then the answer is yes, because
$$P_{ss'}^a = \sum_r p(r,s'|s,a)$$
Question 2. What are the advantages of looking at $q_{\pi}(s,a)$ versus $v_{\pi}(s)$?
The main advantage is that you can derive a policy more easily from $q_{\pi}$:
$$\pi'(s) = \text{argmax}_a q_{\pi}(s,a)$$
Compare with deriving a policy using $v_{\pi}$:
$$\pi'(s) = \text{argmax}_a \sum_{s',r} p(r, s'|s,a)(r + \gamma v_{\pi}(s'))$$
Note that these policies are not necessarily the same as $\pi$ on which the $q$ or $v$ values are evaluated. In fact this is a common situation whilst searching for an optimal policy, and it is possible to show that $\pi'(s)$ will result in same or higher returns as $\pi(s)$ across all states . . . the proof of this is called the policy improvement theorem.
The important thing about the first equation using $q$ is that it does not involve using the MDP model $p(r, s'|s,a)$ directly. This is the basis of model-free RL. Whilst the version using $v$ is more complex (taking more computation) and requires that you know $p(r,s'|s,a)$.
The main disadvantage of looking at $q_{\pi}(s,a)$ is that it has a larger dimension, it maps $S \times A \rightarrow \mathbb{R}$, as opposed to using $v_{\pi}(s)$ which maps $S \rightarrow \mathbb{R}$. So it can take longer to get good approximations of $q$ compared to $v$.