As per the languages listed in the title of your question, Python would probably be the best choice.
There is a list of Python web development frameworks, and you can find a list of popular online projects using Python, as well as some more information about using Python on the web.
A few features you may find interesting (that actually sparked my interest in python):
- Generators
- List comprehension
- Easy multi-threading
- Function and class decorators
- The
with
statement
- List and dictionary unpacking for procedure arguments (I find this awesome)
- Great built-in functions (
enumerate
, zip
, map
, reduce
, etc.)
- Extensive standard library (you will be used to this luxury coming from .Net)
The list goes on. Although C# can already do most of this, some of it is more verbose and more difficult, though not all of it (I'm not fluent in C# myself, I just know a couple of its features theoretically). Even better, Python is interpreted (quickly) so there's no need to re-compile every time you make a change. Similar to C#, Python is supported well on the web and on the desktop, with many libraries and frameworks supporting both kinds of development.
Aside from that, ASP.NET and C#.Net are some good options for web development as well.
Also, as much as everybody hates it, PHP is one of the most popular web programming languages in use, and there exist many frameworks to make PHP less painful to work with. A few: CodeIgniter, CakePHP, Yii, Zend and WASP
found at PHP Frameworks.
It's always good to learn new languages, you can learn a lot more ways to approach the problems you run into. Lots of well-versed developers use idioms from other languages to make their language easier to work with.
However, you should be careful not to invest too much new time in learning languages that aren't going to benefit you at your job. If learning a particular language is going to benefit your productivity and increase the Business Value of your application(s), then go for it; otherwise it will probably be an academic exercise.
Over time learning a language and some new concepts here and there could greatly increase your worth as a programmer, however. But you should be more focused on using your current technology right, and getting into the new stuff when it becomes relevant to your job.
As for finding new jobs, sure, a long list of languages might help you. But what will help you more is being the type of developer that can quickly pick up any language you need to, while applying your experience in previous languages to make you even better in that language.