Here's a very simplified example.
Suppose that at one energy, E1, the Boltzmann distribution predicts that a state will have 100 molecules in it.
In a state of greater energy, E2, the Boltzmann distribution predicts that a state will have 50 molecules in it.
However, suppose only one state has energy E1, but there are 4 states with energy E2. Then there will be 100 molecules with energy E1, but there will be 4*50 = 200 molecules with energy E2.
So, in this case, twice as many molecules will have the greater amount of energy. That is (if the energy was determined by the kinetic energy only), twice as many molecules will have the higher velocity.
Hope this helps -- let's see what further questions that you have.
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