Does new medical insurance coverage automatically become the primary coverage?

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No, I'm checking on the CA State Law, but haven't found it yet. Here's the research I found so far.
From Blue Cross Administrators Manual
Medicare is the primary payor for employees age 65 or older in employer groups with less than 20 employees
When a group has fewer than 20 employees, Blue Cross is considered the secondary payor to Medicare and does not duplicate benefits that might be available under Medicare.
This is from Blue Cross of CA FAQ's
What is Coordination of Benefits (COB)?
A43.Coordination of Benefits (COB) is a provision to coordinate 100% of covered charges between multiple group health insurance and to designate the order in which the multiple carriers are to pay benefits. Under a COB provision, one Plan is determined to be primary and its benefits are applied to the claim. Part or all of the unpaid balance is usually paid by the secondary Plan to the limit of its liability. The coordination provisions apply separately to each member, per calendar year, and are largely determined by California law.  
Here's the phamplet from Medicare
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Can you designate the primary and secondary insurance coverage yourself?

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What is Coverage A in insurance?

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What is the definition of primary coverage in regard to medical insurance?

Often, a person will have "primary" insurance and "secondary" insurance. For example, if you have insurance through your job, and your husband has insurance through his job, t

How is it deemed which insurance coverage is primary and which is secondary?

The answer to that question depends on a few things. 1. Group insurance policies are always primary over personal or self bought You work for ABC company. You ha