Here are examples of nontrivial $A_\infty$-structures extending the product on $\operatorname{Sym}(\mathbb R^3[-1])$ and $\operatorname{Sym}(\mathbb R^5[-1])$, respectively. Below the fold, I have kept my original answer, which got the main ideas right but almost all degrees wrong.
Fix coordinates $\xi_1,\xi_2,\xi_3$ on $\mathbb R^3[-1]$ and set
$$
\mu_3(f_1,f_2,f_3) = \xi_2\xi_3 (\partial_{\xi_1}f_1)(\partial_{\xi_1}f_2)(\partial_{\xi_1}f_3)\ .
$$
This defines a $A_\infty$-structure: Every term in $[\mu_3,\mu_3](f_1,\dots,f_5) = \sum \mu_3(\dots,\mu_3(\dots),\dots)$ contains $\xi_1^2 = 0$ and hence vanishes; similarly, $[\mu_3,\mu_2](f_1,\dots,f_4)$ vanishes if one of the $f_i$ is a multiple of $\xi_2$ or $\xi_3$, and it also vanishes if one of them is the identity since $[-,-]$ preserves normalized Hochschild cochains. Thus the only expression we have to check is
\begin{align*}
[\mu_2,\mu_3](\xi_1,\xi_1,\xi_1,\xi_1) &= \color{red}{-}\xi_1\mu_3(\xi_1,\xi_1,\xi_1) -\mu_3(\xi_1^2,\xi_1,\xi_1) \\
&\ + \mu_3(\xi_1,\xi_1^2,\xi_1) - \mu_3(\xi_1,\xi_1,\xi_1^2) \\
&\ + \mu_3(\xi_1,\xi_1,\xi_1)\xi_1\\
&= -\xi_1\xi_2\xi_3 + \xi_2\xi_3\xi_1 = 0
\end{align*}
(The red sign comes from the Koszul sign rule.)
This $A_\infty$-algebra has a nontrivial Massey product $0\notin \langle\xi_1,\xi_1,\xi_1\rangle = \xi_2\xi_3 + \xi_1A + A\xi_1$ and hence is not formal.
Essentially the same argument applies to the $A_\infty$-structure on $\mathbb R^5[-1]$ defined by the only nontrivial bracket
$$
\mu_3(f_1,f_2,f_3) = \xi_2\xi_3\xi_4\xi_5 (\partial_{\xi_1}f_1)(\partial_{\xi_1}f_2)(\partial_{\xi_1}f_3)\ .
$$
Recall that we can associate to any (cohomologically) graded algebra $(A,\mu_A)$ the Hochschild cochains
$$
C^n(A) = \prod_{p+q = n}\operatorname{Hom}^p(A^{\otimes q},A)
$$
which come equipped with a differential defined by precomposing with the multiplication of cyclic neighbours in the tensor product. As the totalization of a double complex, it also comes with a canonical filtration, namely
$C^n_{\ge m}(A) = \prod_{{\substack{p+q=n\\q\ge m}}} \operatorname{Hom}^p(A^{\otimes q},A)$. The skew-symmetrization of the pre-Lie structure $f\circ g(c_1,\dots,x_{m+n-1}) = \sum_{i=1}^m \pm f(x_1,\dots,g(x_i,\dots,x_{i+n-1}),\dots,x_{m+n-1})$ defines a filtered shifted dgla structure on $C^*(A)$, and $A_\infty$-structures with trivial differential $(A,0,\mu_A,\mu_3,\dots)$ correspond to Maurer-Cartan elements $(\mu_3,\dots)$ in $C^2_{\ge 3}(A)$.
Now consider any such element $\mu$; its component of lowest filtration defines a degree $2$ cohomology class in the associated graded, since $\mathrm d\mu = -\frac{1}{2}[\mu,\mu]$ lies in higher filtration (as $[C^p_{\ge m}(A),C^q_{\ge n}(A)]\subset C^{p+q-1}_{\ge m+n-1}(A)$). If this cohomology class is $0$, i.e. $\mu = \mathrm d\eta$ up to terms of higher filtration, we can act by the gauge symmetry $\mu\mapsto e^{-\eta}\circ\mu = \mu - \mathrm d\eta\, + (\text{higher filtration})$ to obtain an equivalent Maurer-Cartan element which lies in higher filtration. Since the Hochschild cochains are complete with respect to the canonical filtration, the limit of this process is well-defined, i.e. if all obstructions vanish we obtain that our Maurer-Cartan element is gauge equivalent to $0$.
If $A = \operatorname{Sym}(V)$ is the commutative algebra on a graded vector space $V$, we can compute $C^*(A)$ with its filtration explicitly: We have $C^*(A) \simeq \operatorname{Ext}_{A\otimes A^{op}}(A,A)$, and since the multiplication map $A\otimes A^{op}\to A$ is $\operatorname{Sym}$ of the codiagonal $V\oplus V\to V$, we obtain a Koszul resolution $A\simeq (\operatorname{Sym}(V\oplus V\oplus V[1]),\mathrm d)$. Explicitly, we choose a basis $x_i$ of $V$; then the resolution is generated by elements $x_i,x_i'$ in degree $|x_i|$ and $y_i$ in degree $|x_i|-1$, with $\mathrm dy_i = x_i' - x_i''$. (This is where we use characteristic $0$.) It follows that $C^*(\operatorname{Sym}(V))\simeq \widehat{\operatorname{Sym}}(V\oplus V^*[-1])$, where the filtration is given by the degree in the $V[-1]$-variables, and the hat indicates that we take the completion with respect to this filtration.
Now let us specialize to the two cases in your question, namely $V$ is concentrated in degree $-1$ or $+1$. In the second case, $C^*(A)$ is concentrated in nonnegative degrees, and $HH^2(A) := H^2(C^*(A))\cong \operatorname{Sym}^* V^*\otimes \Lambda^2 V$, with the relevant part in $\operatorname{Sym}$-filtration $\ge 3$. In the first case, $V\oplus V^*[-1]$ lives in degrees $-1$ and $2$, and the deformation group is given by $HH^2_{\ge 3}(A) = \prod_{p\ge 3} \Lambda^{2p-2}V\otimes \operatorname{Sym}^p V^*$ and thus also does not vanish. Indeed, Kontsevich's formality theorem shows that Maurer-Cartan elements of $\hbar C^*_{\ge 3}(A)[[\hbar]]$ are in bijection with those of its cohomology, i.e. an infinitesimal deformation can be extended to a formal deformation iff it satisfies the Maurer-Cartan equation in in the cohomology. In some cases, the formal infinite series involve only finitely many terms and therefore give rise to actual deformations, as is the case in the two examples above.
