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Now, this is also a business decision. You have to take into account the costs of development, delivering and maintaining the application on your chosen platform.
Finally, what is the nature of your web application/site. Does your site have any special requirements? Unique business logic that can optimally be achieved on one platform and not the other?
I think there is never a definitive answer. It is all relative to the situation you are in
Personally, I started with ZERO knowledge, and went the FreeBSD/Perl/php route as the initial costs are much lower. Support is a bit more spotty, but Google has helped me figure out every problem I have faced. YMMV
That said, I prefer PHP to ASP for projects I develop myself.
Both technologies can probably do what you want to do. Unless you are working in a strongly MS environment and interfacing with MS backends, why choose ASP/MSSQL?
That being said--it really depends on what you are doing and if there are packages already available that do what you want in PHP or ASP. If there is something there... use it.
MySQL and MSSQL are from the web development point of view nearly identical and also PHP and ASP offer roughly the same type of functionality, although with a different syntax.
The big problem lies in the webserver software IIS versus Apache where Apache is the most versatile of the two. IIS also has a design flaw where URLs are case insensitive which can potentialy give huge duplicate content problems in the search engines. I.e. a page can be indexed as /Page.Html, /page.html, /PAGE.HTML and all other variants available.
If you choose for the Apache webserver, the logical decision is to install PHP and MySQL and use the Linux platform.