Any easy way to add <link rel="xxx" > to header of the front page?

Do some search by don't find idea...

your best bet is to create a custom viewlet: https://docs.plone.org/develop/plone/views/viewlets.html and register it for the interface IPloneSiteRoot

if you're using diazo you can create a rule that inserts the <link> element in <head> only for the frontpage (condition: body class something with PloneSite)

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Or you register your own CSS with the Plone resource registry.

the way the question was asked lead me to think of <link rel="alternate" .../> etc. rather than css. also it was asked to add the link only for the frontpage