The theoretical value is what you should have seen, and the experimental value is what you actually did see.
So, your average experimental value for velocity would be the average of all the velocities you collected in your experiment (assuming you did multiple trials of the same experiment)
Your theoretical value is what you should have observed IN THEORY. So, what you expected to see (even though your actual observations might be different).
In this case, your theoretical value would be what the velocity of the ball (cart, block, etc..) should have been.
Let's say you dropped a ball off of a table and had to find its final velocity... your theoretical value is found by using the equation for velocity with respect to height and gravity (you know the height you dropped it from, you know the accelleration due to gravity, you know the mass of the ball, etc...) so, what SHOULD velocity be by solving the equation?
Your experimental value is what you actually measured--in this case maybe you had a photogate at the floor and were able to measure the velocity of the ball as it went through, that's the experimental value.