Hi, it depends on your field of expertise, for example there are (arguably) two kinds of web programmers (or web developers), front and back end, meaning one deals mainly with the client side of a website or web service and uses mostly JS, CSS, (?)HTML, possibly java too for that, and the other writes software that runs on the server with technologies like Java, JavaScript (check out NodeJS), perl, php, asp...
XML is not a programming language and it most certainly is not a database. A database requires a database management system to read it, and that requires a certain set of features that XML alone does not implement (it would be like comparing Notepad to MySQL).
For web purposes XML is fading away in view of JSon, but it is still in strong use, so again, it depends on what are you working on. However XML is so incredibly use to use that you dont have to worry about learning it, chances are there's a library that converts your XML document into an array (try converting an entire database in an array...) so you dont have to do much work on it.
Then again if you are not developing web sites but web services your front end developer would most likely work on VB or any of the .Net family (unless your program is going to run on linux so then maybe wxWidgets => C++).
I've been working as a web developer related to web sites and information systems for over 6 years, in my every day work I use PHP, JS, CSS, MySQL/SQL oh yeah! MySql, PostgreSQL... they comply with the SQL standard, so you'd do well in paying attention to that instead of "learning MySQL" for example, sure enough there are additions in every DBMS but they all share a common root.
My advise, define your career path first, who knows and you may wind up working with Android or Objective C