I don't know about anything.net or VB.anything, but I believe Perl is definitely suitable for the situation you described.

As you have a client/server environment, I recommend a Web App running on your office intranet. This eliminates the need for an installation. Preferably running on top of Apache. I think it can be set up on IIS, but I don't have a clue how to do that. For an easy server setup, I recommend xampp [apachefriends.org] which comes with Apache, MySQL, and PHP. You'll also need the xampp Perl add-on. It's all very easy to install. You could download and install everything in less than 30 minutes.

... feeding the script to the stations ...
Does this mean a script which the users read over the telephone? That can all come out of a MySQL table.

I don't know how you get the list of callers into the database, but after you do, querying then and prioritizing them according to time of call should be easy.

In all, I think Perl would be very effective for this task. To make it a nice Web App, you'll need to get up to speed on DHTML stuff. You'll need the following, which all comes with xampp :
Apache
ActiveState Perl
  CGI
  DBI
  DBD::mysql
MySQL

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-- GhodMode