The goal is to prove that the subspace spanned by $U^{\otimes n}$ for all $d\times d$ unitary matrices $U$ includes $M^{\otimes n}$ for every $d\times d$ matrix $M$. Here's my attempt to make this as elementary as possible. I'm afraid it's a bit long but hopefully each step is simple enough.
We can first reduce the problem to diagonal matrices, which allows it to be translated to an analogous question for vectors in place of matrices. For a given matrix $M$, consider a singular value decomposition $M = V D W$ where $D$ is diagonal and $V$ and $W$ are unitary. If $D^{\otimes n}$ is contained in the subspace spanned by all $E^{\otimes n}$, where $E$ ranges over all diagonal unitary matrices, then it follows that $M^{\otimes n} = (V D W)^{\otimes n}= V^{\otimes n} D^{\otimes n} W^{\otimes n}$ is contained in the subspace spanned by all $V^{\otimes n} E^{\otimes n} W^{\otimes n} =(V E W)^{\otimes n}$, again as $E$ ranges over all diagonal unitary matrices. Because $VEW$ is always unitary, this establishes the required fact.
We therefore only need to worry about diagonal matrices — so we might as well think about $d$ dimensional vectors instead. Let $\mathbb{T} = \{\alpha\in\mathbb{C}\,:\,\vert\alpha\vert = 1\}$ denote the set of complex units, which are the possible diagonal entries of a diagonal unitary matrix. What we'll prove is that the set $\{u^{\otimes n}\,:\,u\in\mathbb{T}^d\}$ spans the entire symmetric subspace $(\mathbb{C}^d)^{\vee n}$, which includes every vector $v\in(\mathbb{C}^d)^{\otimes n}$ that is invariant under every permutation of its tensor factors (i.e., the action of $\pi_n(\sigma)$ for every $\sigma\in S_n$). This includes every vector of the form $w^{\otimes n}$, and from this we can conclude what we need about diagonal matrices.
Consider an arbitrary symmetric vector $v\in(\mathbb{C}^d)^{\vee n}$, and suppose that $v \perp \{u^{\otimes n}\,:\,u\in\mathbb{T}^d\}$, meaning that $\langle v, u^{\otimes n}\rangle = 0$ for every $u\in\mathbb{T}^d$. We'll show that $v$ must be the zero vector, and that's all we need — for if $\{u^{\otimes n}\,:\,u\in\mathbb{T}^d\}$ spanned a proper subspace of $(\mathbb{C}^d)^{\vee n}$ then there would have to exist a nonzero symmetric vector perpendicular to it.
To this end let us think about the entries of $u$ as variables $Z_1,\ldots,Z_d$. The entries of $u^{\otimes n}$ are therefore monomials in these variables having total degree $n$. When we take the inner product of $v$ with $u^{\otimes n}$ we obtain a multivariate polynomial $P(Z_1,\ldots,Z_d)$ in the variables $Z_1,\ldots,Z_d$, which happens to be a sum of monomials having total degree $n$ (but all we really need is that it's a polynomial). This polynomial is zero when $Z_1,\ldots,Z_d$ all range independently over $\mathbb{T}$ by the assumption that $v \perp \{u^{\otimes n}\,:\,u\in\mathbb{T}^d\}$.
However, the only way that can happen is that $P$ is the zero polynomial. Here's one way to see this. We can write
$$
P(Z_1,\ldots,Z_d) = \sum_{k=0}^n Q_k(Z_1,\ldots,Z_{d-1}) Z_d^k
$$
for polynomials $Q_0,\ldots,Q_n$ in the first $d-1$ variables $Z_1,\ldots,Z_{d-1}$. For every $(\alpha_1,\ldots,\alpha_{d-1}) \in \mathbb{T}^{d-1}$ we find that $P(\alpha_1,\ldots,\alpha_{d-1},Z_d)$ is a univariate polynomial in the variable $Z_d$, and our assumption is that this polynomial takes the value zero everywhere on $\mathbb{T}$. But nonzero univariate polynomials can only have finitely many roots, so this must be the zero polynomial. This implies that the polynomials $Q_0,\ldots,Q_n$ are always equal to zero on $\mathbb{T}^{d-1}$. By applying this argument recursively, effectively eliminating the variables one at a time, we can conclude that $Q_0,\ldots,Q_n$ are all the zero polynomial, and therefore so is $P$.
Finally, because the vector $v$ is symmetric, we know that a lot of its entries must be equal (in general). In particular, if we think of the entries of $v$ as being indexed by tuples $(a_1,\ldots,a_n)$, where $1\leq a_1,\ldots,a_n\leq d$, then we must have
$$
v(a_1,\ldots,a_n) = v\bigl(a_{\sigma(1)},\ldots,a_{\sigma(n)}\bigr)
$$
for every $\sigma\in S_n$. This means that the entry $v(a_1,\ldots,a_n)$ depends only on the number of times each index $1,\ldots,d$ appears in the tuple — or in other words it depends only on the multiset $\{a_1,\ldots,a_n\}$. We can naturally associate the multiset $\{a_1,\ldots,a_n\}$ with the monomial $Z_{a_1}\cdots Z_{a_n}$, and when we take the inner product of $v$ with $u^{\otimes n}$, we're always multiplying these same values that occur as entries of $v$ to the same corresponding monomial appearing as an entry of $u^{\otimes n}$. We've already concluded that our polynomial $P$ is the zero polynomial, and so it follows that every entry of $v$ must be equal to zero. We've shown that $v = 0$ so the argument is complete.