Hi ForMyThunder!
The standard n-simplex has vertices (1,0,0,...,0),(0,1,0,...,0),...,(0,0,0,...,1). Now, given a map [itex]\sigma:\Delta^n\rightarrow X[/itex] of our Delta-complex, then we can call
[tex]\sigma (1,0,0,...,0),~\sigma (0,1,0,...,0),...,\sigma (0,0,0,...,1)[/tex]
are the vertices of these maps. A simplicial complex is such that no two maps [itex]\sigma_\alpha[/itex] and [itex]\beta[/itex] have the same set of vertices!
For example, consider the square [0,1]x[0,1]. Then the points (0,0),(1,0) and (0,1) form a triangle which is homeomorphic to [itex]\Delta^2[/itex], so take that as a first map. The points (1,0),(0,1) and (1,1) also determine a map. Continuing further gives us a simplicial complex, because every collection of points belongs to at most 1 map.
However, if we would take another map from [itex]\Delta^2[/itex] to the triangle (0,0), (1,0), (0,1) and adjoing it to our complex, then there would be two maps with vertices (0,0), (1,0) and (0,1). This would not form a simplicial complex.
Hope that helped!