$\newcommand{\bra}[1]{\left<#1\right|}\newcommand{\ket}[1]{\left|#1\right>}\newcommand{\bk}[2]{\left<#1\middle|#2\right>}$
Let $H$ be a Hilbert space. We call states $\ket{\psi_1}, \dots, \ket{\psi_n} \in H$ perfectly distinguishable if there exists a measurement system $\big\{M_i\big\}_{i=1}^{m}$, with $m\geq n$, such that $|| M_j\ket{\psi_i}||^2 = 1$ if $i = j$ and $|| M_j\ket{\psi_i}||^2 = 0$ otherwise . Show that the states $\ket{\psi_1}, \dots, \ket{\psi_n}$ are perfectly distinguishable exactly when they are mutually orthogonal.
It is not too hard to see that you can construct a measurement system from mutually orthogonal states that satisfy the desired property. (As Nielsen & Chuang outline in Quantum Computation and Quantum Information).
However, I am not really sure how one might go about showing the other direction, i.e. why perfectly distinguishable states are necessarily mutually orthogonal. I am assuming I would have to apply $M_j\ket{\psi_i}$ to $\ket{\psi_j}$ and use properties of the measurement system, along with taking advantage of the Dirac notation, but I have not been able to get myself anywhere useful by doing this.
Edit: The definition of "(finite outcome) measurement" I am using is: a set of operators $\big\{M_i\big\}_{i=1}^{n}$ such that $\sum_{i=1}^{n}M_i^*M_i = I$.