Hi.
Here mentioned the comments for your queries:
1)We would like to know where to associate Home Delivery with a Residential Address & Ground for a Commercial Address??
Comments: You no need to associate, contact fedex tech support they will enable the address validation in your account.
2)How to setup Fedex Home Delivery and standard overnight for residential and ship Fedex Ground or standard overnight for commercial??….Please help!!
Comments: Configure the Fedex shipping in go to admin panel >> system >> configuration >> shipping methods enable the default fedex method and select the service you want.