Disclaimer: As pointed out by several people the original orthogonality condition I was asking about seems to be incorrect so I'm just going to change the question to the orthogonality condition addressed in the answer below.
Let $ \pi_1, \pi_2 $ be distinct irreps of a finite group $ G $. Let $ \chi_1, \chi_2 $ be the corresponding characters. Then we know that
$$
\sum_{g \in G} \chi_1(g) \chi_2(g)^*=0
$$
Dropping the trace (and assuming that $ \pi_1, \pi_2 $ have the same degree in particular $ \pi_1: G \to GL_d(\mathbb{C}) $ , $ \pi_2: G \to GL_d(\mathbb{C}) $ ) consider the sum
$$
\sum_{g \in G} \pi_1(g) \pi_2(g)^*
$$
Is there some sort of "orthogonality" here as well? In other words, for two distinct irreps $ \pi_1,\pi_2 $ of the same degree do we have that
$$
\sum_{g \in G} \pi_1(g) \pi_2(g)^*
$$
is the zero matrix?
Of course this is true for degree $ 1 $ by character orthogonality. Is it true for higher degree irreps?
Let's generalize. Suppose $(V_1,\pi_1)$ and $(V_2,\pi_2)$ are two irreps of $G$. Define
$$ T(M)=\frac{1}{|G|}\sum_{g\in G} \pi_1(g)M\pi_2(g^{-1}). \tag{$\color{green}{\triangle1}$}$$
Observe $T$ is a linear operator on the vector space $\hom(V_2,V_1)$. Your original question was when $\dim V_1=\dim V_2$ and $M=I$, but this restriction is not necessary.
Observe that for any $M\in\hom(V_2,V_1)$, the operator $T(M)$ is equivariant, i.e. for any $a\in G$,
$$ \pi_1(a)T(M)=T(M)\pi_2(a), $$
by reindexing the summation and using socks-and-shoes. By Schur's lemma, if $\pi_1\not\cong\pi_2$ there are no intertwiners, so $T(M)=0$ for all $M$.
If $\pi_1=\pi_2$ then $T(M)=\lambda(M)I$ for some linear scalar function $\lambda(M)$ of $M$. Taking the trace in the definition $({\color{green}\triangle})$ yields $\mathrm{tr}\,M=d_1\lambda(M)$, where $d_1$ is the dimension, so
$$ T(M)=\delta_{\pi_1\pi_2}\frac{\mathrm{tr}\,M}{d_1}I. \tag{$\color{green}{\triangle2}$}$$
Note this implies the worry about coordinate-dependence expressed in the comments is not a problem. Indeed, if we define the conjugate $\pi_1'(g)=A\pi_1(g)A^{-1}$ for some $A\in\mathrm{GL}(V_1)$, and define $T'$ accordingly, we get $T'(M)=AT(A^{-1}M)$, so the same conclusions holds for $T'$ as $T$, and similarly if we use a conjugate of $\pi_2$ as well (assuming $\pi_1\not\cong\pi_2$).
Recall we have an isomorphism of reps $\hom(V_2,V_1)\cong V_1\otimes V^\ast_2$. Say we view $V_1,V_2$ as spaces of column vectors. We can view $V_2^\ast$ either as the same vector space and apply $\pi_2^\ast(g)=\pi_2(g^{-1})^T$ from the left, or we can view it as a space of row vectors on which we apply $\pi_2(g^{-1})$ from the right. This allows us to reinterpret $T$ from the linear operator $(\color{green}{\triangle1})$ on $\hom(V_2,V_1)$ to a linear operator $({\color{Magenta}\diamondsuit})$ on $V_1\otimes V_2^\ast$ ("transport of structure") given by
$$ T=\frac{1}{|G|}\sum_{g\in G} \pi_1(g)\otimes \pi_2(g^{-1})^T, \tag{$\color{Magenta}\diamondsuit$}$$
where we interpret $V_2^\ast$ as comprised of column vectors. If we view $V_2^\ast$ instead as comprised of row vectors, then the isomorphism $V_1\otimes V_2^\ast\cong\hom(V_2,V_1)$ is given by $v_1\otimes v_2^T\mapsto v_1v_2^T$ and we don't transpose $\pi_2(g^{-1})$ anymore; this is why $\pi(g^{-1})$ does not appear with a transpose in $({\color{green}\triangle})$.
We can generalize further still to include your previous question:
$$ T(M)=\frac{d_3}{|G|}\sum_{g\in G}\chi_3(g^{-1})\,\pi_1(g)M\pi_2(g^{-1}), \tag{$\color{blue}☾$}$$
where a third irrep $(V_3,\pi_3)$ has character $\chi_3=\mathrm{tr}\,\pi_3$ and dimension $d_3=\chi_3(e)$. Now, $T$ is the isotypical projector onto the $V_3$-component of $\hom(V_2,V_1)$ as a rep. For $\pi_3$ trivial this re-establishes the above conclusions.
One textbook application of $T(M)=\delta_{\pi_1\pi_2}\frac{\mathrm{tr}\,M}{d_1}I$ from $({\color{green}\triangle})$ is Schur Orthogonality for Matrix Coefficients. This was relevant to your next question.
If we pick the standard basis matrix $M=e_{jk}$ and look at the $i\ell$ entry of $T(M)$, on the one hand we get $\delta_{\pi_1\pi_2}\frac{\mathrm{tr}\,e_{jk}}{d_1}I_{i\ell}=\delta_{\pi_1\pi_2}\delta_{jk}\delta_{i\ell}/d_1$ from ($\color{green}{\triangle2}$). On the other hand, from ($\color{green}{\triangle1}$) we get
$$ \frac{1}{|G|}\sum_{g\in G}\sum_{j',k'}\pi_1(g)_{ij'}(\delta_{jj'}\delta_{kk'})\pi_2(g^{-1})_{k\ell}. $$
Assuming $\pi_2$ is unitary so $\pi_2(g^{-1})=\pi_2(g)^\dagger=\overline{\pi_2(g)}^T$, this simplifies to
$$ \frac{\delta_{\pi_1\pi_2}\delta_{i\ell}\delta_{jk}}{d_1} = \frac{1}{|G|}\sum_{g\in G}\pi_1(g)_{ij}\overline{\pi_2(g)}_{\ell k}. \tag{$\color{Purple}{\square}$}$$
These are the orthogonality relations.
If we (wlog) unitarize our irreps, then $\pi_2(g^{-1})^T=\overline{\pi_2(g)}$. Then we may set
$$ S(M)=\frac{1}{|G|}\sum_{g\in G}\pi_1(g)M\overline{\pi_2(g)}. \tag{$\color{orange}{\circ1}$}$$
The $i\ell$ matrix entry of $S(M)$ is given by
$$ S(M)_{i\ell} \,=\, \frac{1}{|G|}\sum_{g\in G}\sum_{j,k}\pi_1(g)_{ij}M_{jk}\,\overline{\pi_2(g)}_{k\ell} $$
$$ =\, \sum_{j,k}M_{jk}\big(\frac{1}{|G|}\sum_{g\in G} \pi_1(g)_{ij}\overline{\pi_2(g)}_{k\ell}\big) $$
$$ =\, \sum_{j,k}M_{jk}\frac{\delta_{\pi_1\pi_2}\delta_{ik}\delta_{j\ell}}{d_1} \,=\, \frac{\delta_{\pi_1\pi_2}}{d_1} M_{\ell i}. $$
Therefore we may conclude
$$ S(M)=\frac{\delta_{\pi_1\pi_2}}{d_1}M^T. \tag{$\color{orange}{\circ2}$}$$