This is not possible(switch to secondary) with the current versions of the PI Web API. We already have an internal Work Item that tracks the issue.
You can also post your enhancement ideas, suggestions and feedback about our products at https://feedback.osisoft.com/ (you get to vote too) and is actively monitored by our product managers and developers.
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Currently there is no method to pick a collective member to connect per se. However, PI Web API will still follow the connect priority in SDK settings.
Please take a look into the PI Web API service node's SDK setting. More information on this is in Specify the server connection order for a PI Data Archive collective LiveLibrary document.