For a fixed $n$, you can solve the problem via integer linear programming. For $j \in [n]$, let binary decision variable $x_j$ indicate whether $j\in S$. For $0\le j_1\le j_2 \le n$, let binary decision variable $y_{j_1,j_2}$ indicate whether both $j_1$ and $j_2$ are in $S$. The problem is to minimize $\sum_j x_j$ subject to
\begin{align}
\sum_j y_{j,i-j} &\ge 1 &&\text{for $i \in [2n]$}\\
y_{j_1,j_2} &\le x_{j_1}\\
y_{j_1,j_2} &\le x_{j_2}
\end{align}
I didn't try to find all optimal solutions, but here is one for each $n \le 50$:
n m optimal S
1 2 {0,1}
2 3 {0,1,2}
3 4 {0,1,2,3}
4 4 {0,1,3,4}
5 5 {0,1,2,4,5}
6 5 {0,1,3,5,6}
7 6 {0,1,2,4,6,7}
8 6 {0,1,3,5,7,8}
9 7 {0,1,3,5,7,8,9}
10 7 {0,1,3,5,7,9,10}
11 8 {0,1,3,5,7,9,10,11}
12 8 {0,1,3,5,7,9,11,12}
13 8 {0,1,2,5,8,11,12,13}
14 9 {0,1,3,5,7,9,11,13,14}
15 9 {0,1,3,4,9,11,12,14,15}
16 9 {0,1,2,5,8,11,14,15,16}
17 10 {0,1,3,5,7,8,13,14,16,17}
18 10 {0,1,3,5,6,12,13,15,17,18}
19 10 {0,1,2,5,8,11,14,17,18,19}
20 10 {0,1,3,4,9,11,16,17,19,20}
21 11 {0,1,3,5,6,13,15,16,18,20,21}
22 11 {0,1,2,3,7,11,15,19,20,21,22}
23 12 {0,1,3,5,6,13,15,16,18,20,22,23}
24 12 {0,1,3,5,7,8,16,17,19,21,23,24}
25 12 {0,1,3,4,9,11,15,17,21,22,24,25}
26 12 {0,1,3,4,9,11,15,17,22,23,25,26}
27 12 {0,1,3,5,6,13,14,21,22,24,26,27}
28 13 {0,1,2,3,5,9,13,17,21,25,26,27,28}
29 13 {0,1,3,4,9,11,16,18,23,25,26,28,29}
30 13 {0,1,3,4,6,10,14,19,21,26,27,29,30}
31 14 {0,1,2,4,7,9,10,15,20,22,27,28,30,31}
32 13 {0,1,3,4,9,11,16,21,23,28,29,31,32}
33 14 {0,1,3,5,6,12,13,20,21,27,28,30,32,33}
34 14 {0,1,2,3,7,11,15,19,23,27,31,32,33,34}
35 14 {0,1,3,5,6,13,14,21,22,29,30,32,34,35}
36 14 {0,1,3,4,9,11,16,20,25,27,32,33,35,36}
37 15 {0,1,3,4,7,9,14,16,21,26,28,33,34,36,37}
38 15 {0,1,2,3,4,9,14,19,24,29,31,34,35,37,38}
39 15 {0,1,3,4,9,11,16,20,25,30,35,36,37,38,39}
40 15 {0,1,3,4,5,8,14,20,26,32,35,36,37,39,40}
41 16 {0,1,3,5,6,11,12,19,20,27,28,35,36,38,40,41}
42 16 {0,1,3,4,7,8,13,18,23,28,33,35,38,39,41,42}
43 16 {0,1,3,4,5,8,14,20,26,29,35,38,39,40,42,43}
44 16 {0,1,3,5,7,8,17,18,26,27,36,37,39,41,43,44}
45 16 {0,1,3,4,9,11,16,20,25,29,34,36,41,42,44,45}
46 16 {0,1,3,4,5,8,14,20,26,32,38,41,42,43,45,46}
47 17 {0,1,2,5,8,9,10,15,21,27,33,39,42,43,44,46,47}
48 17 {0,1,3,4,5,8,14,20,26,32,38,39,43,45,46,47,48}
49 17 {0,1,3,4,5,8,14,20,26,32,38,41,45,46,47,48,49}
50 17 {0,1,3,4,9,11,16,20,25,30,34,39,41,46,47,49,50}