I don't know Relais San Rocco, but I saw the map on its web-site and I have a suggestion for you: forget bicycles!
I spent some holidays in Moneglia (that is the village closed to Riva Trigoso beyond the tunnel) and I know well that the street to reach this place is rising, it starts to uphill at the first curve and will continue for 2 km (as indicated on the website)... bycicles are not raccomended!
I don't remember where is the station in Riva Trigoso (I stayed there many years ago) and you are right about the parking availability in the proximity to the station, but I think it is better to consider 5 minute walk (if you find to park not so closed to the station) instead of climb the hill by bycicle.
Have a nice holiday and enjoy 5 Terre!
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