To address this specific case you may identify the pattern and use String.replaceAll
method like this:
String usersWithDepartment = jsonstring.replaceAll(
"(\"Users\":\\s*\\[)", // find a pattern for "Users" element
"\"Department\": \"Accounting\",\n $1" // add a prefix and keep the group $1 as is
);
System.out.println(usersWithDepartment);
This is a quick fix and of course more appropriate approach is to use some JSON processing library as mentioned in the comments.
update
If several occurrences of \"Users\"
array are possible in the input string and you need to add the prefix only to the first occurrence, the regexp should be changed to:
String usersWithDepartment = jsonstring.replaceAll(
"(?s)(\"Users\":\\s*\\[.*$)", // grab entire string, enable multiline selection
"\"Department\": \"Accounting\",\n $1" // add prefix
);