There are always derivations of the form $\delta_b(a) = ab - b\varepsilon(a)$ for $b \in R[G]$, which are called inner derivations. Derivations modulo inner derivations are classified by the first group cohomology with coefficients in the $G$-module $R[G]$, $H^1(G,R[G])$.
In the special case $R=\mathbb Z_2$, Stallings defined a group to have infinitely many ends if $H^1(G,\mathbb Z_2[G])$ has dimension $\geq 2$, in which case it is automatically infinite dimensional. A group has two ends $H^1(G,\mathbb Z_2[G])$ is one-dimensional and one end if $H^1(G,\mathbb Z_2[G])$ vanishes. (See John Stallings, On Torsion-Free Groups with Infinitely Many Ends, Ann. of Math., 1968 vol. 88 (2) pp. 312-334).
Stallings proved that a finitely generated group $G$ has more than one end if and only if the group $G$ admits a nontrivial decomposition as an amalgamated free product or an HNN extension over a finite subgroup. (See Wikipedia.) In that sense, there is a perfect understanding of the class of groups you are looking for.
Fundamental groups of surfaces have one end, so that there exist no interesting derivations, at least for $R=\mathbb Z_2$. Computations for PID's are similar, see Section 13.5 in
Ross Geoghegan, Topological Methods in Group Theory (Graduate Texts in Mathematics), Springer.
This book also contains a whole chapter about the structure of $H^*(G,R[G])$ and its relation to the the topology of the universal cover $EG$ of the classifying space of $G$.