As suggested by you I am posting my (as of now tentative!) answer:
To construct a free resolution for $k$ over $k[x]/\langle x^2 \rangle$ we proceed as in the proof of the theorem that every $R$-module has a free (and hence projective) resolution:
We observe that $k$ is generated by $S = \{1\}$. Hence, to get a surjective map from a free module to $k$ we take the free module over $\{1\}$, $F(S) = F(\{1\}) = k[x]/\langle x^2 \rangle$, and define a map as follows: $ \pi: F(\{1\}) \to k$ $ a_0 + a_1 x + \langle x^2 \rangle \mapsto a_0$
The kernel of $\pi$ is $\langle x \rangle$. Next we produce the free module $F(\operatorname{Ker}{\pi}) = F(\langle x \rangle)$ and define a map $ \pi_1: F(\langle x \rangle) \to F(\{1\})$ $ e_{ax} \mapsto ax$ $\operatorname{Ker}{\pi_1} = \{0\}$ and $\operatorname{Im}{\pi_1} = \operatorname{Ker}{\pi} = \langle x \rangle$.
Hence we have an exact sequence $ 0 \to F(\operatorname{Ker}{\pi}) \xrightarrow{d_1 = \pi_1} F(\{1\}) \xrightarrow{d_0 = \pi} k \to 0$
We chop off $k$ and apply $\operatorname{Hom}{(-,k)}$ to get $ 0 \xrightarrow{\overline{d_0}=0} \operatorname{Hom}{(F(\{1\}),k)} \xrightarrow{\overline{d_1}} \operatorname{Hom}{(F(\operatorname{Ker}{\pi}),k)} \xrightarrow{\overline{d_2}=0} 0$
Now we see that for $i \geq 3$, $\operatorname{Ext^i}{(k,k)} = 0$ since the modules in the chain are all $0$. For $i = 2$, the sequence is exact and we also get $\operatorname{Ext^2}{(k,k)} = 0$. For $k=0$ we know that $\operatorname{Ext^0}{(k,k)} = \operatorname{Hom_{k[x]/\langle x^2 \rangle}}{(k,k)}$.
To compute $\operatorname{Ext^1}{(k,k)} = \operatorname{Ker}{\overline{d_1}}$ we have to compute $\overline{d_1}$.
For this we want to know when given $\varphi \in \operatorname{Hom}{(k[x]/\langle x^2 \rangle, k)}$ we have $\varphi \circ d_1 = 0$. This is true when $\varphi$ is zero on the image of $d_1$ and since the image of $d_1 = \langle x \rangle$, this is true for all $\varphi$ that are zero on $\langle x \rangle$.
I'm not entirely sure how to write this but perhaps we can write this set as $\operatorname{Hom}{(R/\langle x \rangle, R/\langle x \rangle)} \subset \operatorname{Hom}{(R, R/\langle x \rangle)}$ where $R = k[x]/ \langle x^2 \rangle$?