Consider first a special case: x1 + x2 = 10.
The idea is basically this: suppose you have 10 identical (indistinguishable) balls and two baskets A and B. You want to distribute these 10 balls in the two baskets so that each basket can have any number of balls. How many ways can you do so? Or how many distributions exsist?
Note that the baskets have names. So putting (say) 2 balls in A and 8 in B is not the same as putting 2 in B and 8 in A. (We are talking about ordered pairs).
Transform further the problem as follows: Lets put all the balls in a row:
o o o o o o o o o o
We take a spearator: | . Wherever I put this separator among the balls, the situation will correspond to a way of distributing balls. The balls on the left will always go to bag A and to the right will always go to B. For instance,
o o o | o o o o o o o
corresponds to 3 ball in A and 7 in B. Similarly, the situation
| o o o o o o o o o o
correspond to no ball in A and 10 balls in B. Now we can easily see that the separator can be placed at 11 positions. And accordingly there are 11 ways of distribution of the balls: (0,10), (1,9), (2,8), (3,7), (4,6), (5,5), (6,4), (7,3),(8,2),(9,1),(10,0) where the first number corresponds to balls in A and second to balls in B.
Now, if we assign the number of balls in A to the variable x1 and the numbers of balls in B to x2, then, effectively we found out the number of non-negative integral solutions of x1 + x2 = 10.
Now, consider the general problem: find the number of non-negative integral solution of the equation
x1 + x2 + x3 + . . .+xk =n
Here, arguing as before, we place the n balls in a row:
o o o o o o . . . . o
Since we want to partition in to k baskets, we require k-1 separators. Now, the question is effectively to find out how many ways of placing these identical separators are? That is not a very difficult business. Effectively, we have (n + k -1) objects (n balls and k-1 separators) out of which n are identical of one kind and the remaining (k-1) are identical of another kind. How many ways can we arrange them in a row. The answer is straightforward:

that is n+k-1Cn.
Hence, this must be the number of non-negative integral solution of the general equation.