the most familiar examples of vector spaces, are the real plane, and R^3, which we can imagine as being an idealized version of the space we live in.
the usual way to identify a point in the plane or 3-space, is to give it "coordinates". and there is a 1-1 correspondence between a point's coordinates, and the usual way of describing "arrows" in terms of "unit vectors" such as i,j,k:
(x,y,z) <--> xi + yj + zk.
note the plus signs on the right-hand side. this is a different kind of addition than that between ordinary real numbers.
now, in the most general case, we have 2 structures, a field F, and the vector space V. without going into too much detail about what exactly a field is, a field is a set of numbers where one can do all the arithmetic you learned in high-school. normally, one is most interested in real or complex numbers (although other fields are sometimes used).
in some ways, the vector space V itself has LESS structure than the field, as we can (in general) only ADD (and subtract) vectors. what distinguishes the vector space V from just an additive structure, is the way that the field interacts with it: the scalar multiplication.
with scalar multiplication, we can "multiply" a vector by a field element (scalar). intuitively, you can think of this as "stretching", although in the general case of an arbitrary field, this does not always fit perfectly (what does it mean to "stretch by 2+2i"?). in any case, what we get from multiplying a vector by a scalar, is another vector.
the other "rules" (technically, axioms) for a vector space are to ensure that "scalar multiplication" and "vector addition" are compatible. a vector space is anything that satisfies these rules (usually there are 10 of them. some books have a different number).