Approval cycles are saved behind users on the page "Users" or behind cost centers on the page "Cost Centers". If a saved expense has a cost center that has an approval cycle behind it, the expense will follow this cost center's cycle instead of the cycle saved behind the user.
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The approval cycle may contain as many people as needed. You can add more approvers by pressing the button "+add approver".

You can also choose in which order people appear in the approval cycle. If you choose the "Then" rule, person A has to approve the expense before it goes to B's approval. With rule "Or", only A or B has to approve the expense.