Let $a_i,b_i\in\{0,\ldots,9\}$ be the decimal digits of $A$ and $B$
$$A=\sum_{i=0}^aa_i10^i,
\qquad\text{ and }\qquad
B=\sum_{i=0}^bb_i10^i,$$
with $a_a\neq0$ and $b_b\neq0$. Then the digit sums of $A$ and $B$ are
$$\sigma(A)=\sum_{i=0}^aa_i,
\qquad\text{ and }\qquad
\sigma(B)=\sum_{i=0}^bb_i.$$
Without loss of generality $B\leq A$, so that $b\leq a$, and hence setting $b_i:=0$ for $i>b$ yields
$$A+B
=\sum_{i=0}^aa_i10^i+\sum_{i=0}^bb_i10^i
=\sum_{i=0}^a(a_i+b_i)10^i
=\sum_{i=0}^cc_i10^i,$$
for some uniquely determined $c_i\in\{0,\ldots,9\}$, and the digit sum of $A+B$ equals
$$\sigma(A+B)=\sum_{i=0}^cc_i.$$
Now we can carry out the addition place by place as we learned in elementary school. Let $x_i\in\{0,1\}$ denote the carry to the $i$-th place, so that in particular $x_0=0$, and $x_{i+1}=1$ if and only if $a_i+b_i+x_i>9$. Then we can distinguish two cases:
- If $a_i+b_i+x_i\leq9$ then $c_i=a_i+b_i+x_i$, and $x_{i+1}=0$.
The digit sum remains unchanged.
- If $a_i+b_i+x_i>9$ then $c_i=a_i+b_i+x_i-10$ and $x_{i+1}=1$. The digit sum decreases by $9$.
This shows that $\sigma(A+B)\leq\sigma(A)+\sigma(B)$, and equality holds if and only if there are no carries.
Given $N=\sum_{i=0}^nn_i10^i$ with $n_i\in\{0,\ldots,9\}$ and $n_n\neq0$ we can take
$$A=10^n\qquad\text{ and }\qquad B=N-A,$$
to achieve $\sigma(N)=\sigma(A)+\sigma(B)$, as there are clearly no carries. This example fails if and only if $B=0$, i.e. if and only if $N=10^n$ for some $n\in\Bbb{N}$.
If $N=10^n$ then $A=B=5\cdot10^{n+1}$ shows that the minimum sum of digit sums is at most $10$. If the digit sums of $A$ and $B$ are less than $10$ then $A=k\cdot 10^a$ and $B=l\cdot10^b$ for some $a,b\in\Bbb{N}$ and $k,l\in\{1,\ldots,9\}$ and hence to get $A+B=10^n$ we must have $a=b=n-1$ and $k+l=10$, which shows that the minimum sum of digit sums is indeed $10$.
Finally, note that if $n=0$ then $N=10^0=1$ then $N$ cannot be written as the sum of two positive integers, and hence the minimum does not exist.