By simplicial category here I mean simplicially enriched category, i.e. all $Hom$-sets are simplicial sets and compositions are morphisms of simplicial sets.
My question is the following. Suppose I have a category, which I can simplicially enrich. Why would that be useful? What can I do with this extra-structure? What useful information about my category I can obtain using that?
I know that I can compute homotopy groups of $Hom$-sets. Then fundamental group of $Hom(X,Y)$ will classify morphisms between $X$ and $Y$ up to homotopy. I am not sure what will higher groups mean. And I am not sure if it is the most natural thing to do with simplicial category.
Thank you very much for your help!
Well, with simplicial sets you can do homotopy theory, and they are closely related to topological spaces (via the adjunction given by the geometric realization and the singular set). Whereas plain categories are just abstract algebraic gadgets, simplicial categories are really geometric objects. For example, as you have already observed, one can look at the homotopy groups of the hom sets.
Here is a basic (and sort of universal) example: If $n \in \mathbb{N}$, we have a simplicial category $\mathfrak{C}[n]$ with objects $\{0,\dotsc,n\}$, and the simplicial set of morphisms $i \to j$ is the nerve of the poset $\{J \subseteq \{i,\dotsc,j\} : i \in J, j \in J\}$. It is a good exercise to write down the composition of the morphisms, etc. By abstract nonsense, we then get a functor $\mathfrak{C}[-]$ which maps each simplicial set $K$ to some simplicial category $\mathfrak{C}[K]$, and this functor is left adjoint to some simplicial nerve functor. Some details can be found in the beginning of Lurie's HTT. There you also find that simplicial categories (whose morphism sets are Kan) model $(\infty, 1)$-categories.