On the following code:

mov esi, offset Vec
mov eax, [esi]

Esi contains the 1st position of the vector and Eax contains the 1st number of the same vector.

And here:
mov edi, offset (vec + 4)
mov ebx, [edi]

Edi gets the 2nd position of the vector and ebx contais the 2nd number or is it incorrect?

Consider it to be DWORDS.