It does not work the way you want it to work.
One agent can be a member of one and only one agent pool. The agent pool exists at the server level , and not at the Team Project Collection level.
One agent queue is associated with one and exactly one agent pool. However, agent pools can refer to different agent queues across Team Project Collection boundaries.
So, the result of this is that you can share agent pools with several collections of team projects.
There is a difference in VSTS, but less relevant - you cannot have several Team Project collections, so the agent pool and agent queue are more or less equivalent, you just need to get around both of them.
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: https://msdn.microsoft.com/en-us/Library/vs/alm/Build/agents/admin