JSON.stringify() returns a String so your question is incorrect. Item is not an Array.
const Item = '["Basic, JavaScript, PHP, Scala"]';
Therefore you should not use it. Instead simply return the array a in your function:
function loadDataToGridChiefComplaint() {
  var tHRNo = document.getElementById("lblpthrno").value;
  var tOPDNo = document.getElementById("lblptopd").value;
  var localKeyChief = tHRNo + '-' + tOPDNo + '-ChiefComplaint';
  return localStorage.getItem(localKeyChief); // <-- no use of JSON.stringify()
}
This way loadDataToGridChiefComplaint() is the array ["Basic, JavaScript, PHP, Scala"], it has a single element of type String that you can access with the bracket notation Item[0]:
const Item = ["Basic, JavaScript, PHP, Scala"];
console.log(Item[0]);
 
 
So in order to convert the string Item[0] into an array, use the .split method:
String.split(separator)
The split() method splits a String object into an array of strings by separating the string into substrings, using a specified separator string to determine where to make each split.
MDN Web Docs
const Item = ["Basic, JavaScript, PHP, Scala"];
console.log(Item[0].split(', '));
 
 
If you can't modify this function you can use the opposite operation of JSON.stringify which is JSON.parse to convert the string back to an array:
const ItemString = '["Basic, JavaScript, PHP, Scala"]';
ItemArray = JSON.parse(ItemString);
And then use .split (like the previous example) to get the array of strings.