I recommend I.M. Isaacs's Character Theory of Finite Groups to see finite groups from the point of view of their characters.
I couldn't think of a really short example of finding a character table of an unknown group, but I relate a story that can be very briefly summarized as: "Here is an argument in a textbook showing how to uniquely classify two simple groups by the centralizer of an involution. People did that a lot with known simple groups, until Janko found a previously unknown simple group." I only tell the textbook part.
Often we don't need to compute the entire character table to determine how to construct the group. One class of result I found interesting were the "recognition theorems" which often have a large character theory step. However, in order to have an answer that is shorter, I chose an earlier recognition theorem, theorem 7.10 from Isaacs's book:
Suppose a finite perfect group $G=G'$ contains an element $\tau$ of order 2 whose centralizer $C_G(\tau)$ is a dihedral group of order 8. Then $G$ itself must be the 3x3 general linear group $\operatorname{GL}(3,2)$ of order 168, or the degree 6 alternating group $A_6$ of order 360.
Sketch of proof: Let $M \subset D=C_G(\tau)$ be cyclic of order 4 and centralizing $\tau$. Then $M$ is a "trivial intersection" set (similar to Frobenius complements if you've read about those) in that $M \cap M^x = \begin{cases} M & \text{if } x \in N_G(M)=C_G(\tau) \\ 1 & \text{otherwise}\end{cases}$.
Now class functions on $D=C_G(\tau)$ which vanish on $M$ have a very nice isometry property: If $\theta,\phi$ are class functions on $C_G(\tau)$ which vanish on $M$ and $\theta(1)=0$, then the induced character $\theta^G(x) = \theta(x)$ doesn't change for $x\in D$, and moreover neither does the inner product $[\theta^G,\phi^G] = [\theta,\phi]$.
This lets us deduce part of the character table of $G$ from that of $C_G(\tau)$
(I consider that statement to more or less be my answer to your question, but I think it helps to see a little more of how this actually works.)
In particular, take one of the two Galois conjugate faithful linear characters of $M$, call it $\lambda$, then $\theta=(1_M-\lambda)^D$ is a class function on $D$, $\theta(1)=0$, and $\theta$ vanishes on $D \setminus M$ by the formula for induced character. Since $[\theta,\theta]=3$ by an explicit calculation in $D$ (a very small group with an easy character table), we also have $[\theta^G,\theta^G] = 3$ which is now occurring in an unknown group $G$. This means we can write $\theta^G = 1_G + \chi - \psi$ for irreducible characters $\chi,\psi$ of $G$. Since $\theta^G(x) = \theta(x)$ for $x \in D$, we can nearly compute the values of $\chi$ and $\psi$ on $D$!
In $D$, we have $\theta(1)= 0$ and $\theta(\tau)=4$ (again easy calculations in a tiny group), so in $G$ we have $0 = \theta^G(1) = 1 + \chi(1) - \psi(1)$ and $4 = 1 + \chi(\tau) - \psi(\tau)$.
(Isaacs now uses a class function that counts solutions of equations, a technique from Frobenius, to show that:)
$|G|=\dfrac{2^8}{\frac{1^2}{1} + \frac{\chi(\tau)^2}{\chi(1)} - \frac{\psi(\tau)^2}{\psi(1)}}$
A simpler argument shows $|D| \geq 1 + \chi(\tau)^2 + \psi(\tau)^2$
Now a little number crunching finds all possible values of $\chi(\tau)$ and $\psi(\tau)$ which gives all possible orders of $G$: $|G|=168$ or $|G|=360$. Since perfect groups of such small order are quite rare, we have it must be one of the two well-known simple groups.
So this doesn't exactly answer your question: instead of using a character table to find an unkown group, we use it to show a potentially unknown group is actually on old friend. This sort of thing happened several times until Janko accidentally broke it when trying $C_G(\tau) = C_2 \times A_5$ and we found our first new sporadic simple group in a hundred years. The part of the argument I've highlighted here is echoed on page 153 of Janko's 1966 Journal of Algebra paper -- I believe I learned these steps from Suzuki's CA papers, but I can't seem to find my notes at the moment.