You have to make friends with PlistBuddy. The defaults command is not enough. See man PlistBuddy for details. And yes, case is important here. Oh, and you need to path to the tool like /usr/libexec/PlistBuddy. Here is an example, used to modify Time Machines backup Interval:
/usr/libexec/PlistBuddy -c "Set :LaunchEvents:com.apple.xpc.activity:com.apple.backupd-auto:Interval 21600" /System/Library/LaunchDaemons/com.apple.backupd-auto.plist
Please note that if the keys do not exist, you will likely need to string, multiple PlistBuddy commands together, mixing the Add and Set verbs.
Reid
Apple Consultants Network
Apple Professional Services
Author "Mavericks Server – Foundation Services" :: Exclusively available in Apple's iBooks Store