A simple example is a set with four elements $S = \{a, b, c, d\}$. We'll define a partial order so that $a$ is the smallest element, $d$ is the largest element, and $b$ and $c$ are intermediate elements that are incomparable with each other. The relation $R \subset S \times S$, where $(x,y) \in R \Leftrightarrow x \leq y$ is given by
$$
R = \{(a,a), (a,b), (a,c), (a,d), (b,b), (b,d), (c,c), (c,d), (d,d)\}.
$$
I'll leave it for you to check that this is really is a partial order.
The important thing to note is that neither $b \leq c$ nor $c \leq b$ is true, so $R$ is not a total order.
EDIT: As A. Rex astutely points out in the comments, the simplest example would be to take just $S = \{b,c\}$ with the partial order relation $R = \{(b,b), (c,c)\}$. Then $b$ and $c$ are incomparable, so $R$ is not a total order.