Given a Hilbert space $\mathcal{H}_N$, a state $\rho$ is a maximally mixed state if it can be written as $\rho = \frac{1}{N} \sum_{i=1}^N |b_i\rangle \langle b_i |$ for some (any in fact) orthonormal basis $\{b_i\}$ of $\mathcal{H}_N$.
Consider now any density matrix $\sigma$, representing some quantum mixed state. Assume you have a quantum circuit that outputs 1 with probability $\geq 2/3$ on input $\sigma$. I have seen some proofs in quantum computing in which the input of the circuit is set to the maximally mixed state $\rho$ instead, and then the probability to output 1 is said to be $\geq 2/3 \cdot 1/N$. See this paper for instance (section 6, page 15, proof of theorem 20).
I agree that if $\sigma$ is a pure state $\sigma = |\psi \rangle \langle \psi |$, then we can find other vectors $|b'_2\rangle, \dots, |b'_N\rangle$ such that $\{|\psi\rangle,|b'_2\rangle, \dots, |b'_N\rangle\}$ is an orthonormal basis of $\mathcal{H}_N$. Thus, the maximally mixed state can be written as $\rho = \frac{1}{N} \left(\sigma + \sum_{i=2}^N |b'_i\rangle \langle b'_i |\right)$, and we indeed get $\sigma$ with probability $1/N$ if the input of our circuit is $\rho$ (thus the probability of having $1$ is $\geq 2/3 \cdot 1/N$). However, I don't know how to prove it when $\sigma$ is mixed.