You can do this by checking On Control Resolved Users Changed
event for the Client People picker. Please find more info here for Client People Picker Events.
You can try following script block to check if user is already entered in people picker.
Put this script at the end of initializePeoplePicker
function definition as defined in your mentioned link
this.SPClientPeoplePicker.SPClientPeoplePickerDict.peoplePickerDiv_TopSpan.OnUserResolvedClientScript = function (peoplePickerId, selectedUsersInfo) {
console.log('inside OnUserResolvedClientScript');
var users = selectedUsersInfo;
for(var i = 0; i < users.length - 1; i++){
if(users[users.length - 1].Key == users[i].Key){
alert("User already exists");
// Do something else...
}
}
};