The size of the Extra Large (XL) virtual machine provides 14 GB of RAM. This applies to both virtual machines (IaaS) and web / worker roles (PaaS). There are no other VM sizes that provide more RAM. There is nothing you can do to add 2 extra GB.
UPDATE April 16, 2013 : There are now two new sizes: 28 GB / 4-core and 56 GB-8-core, available for virtual machines (not for cloud services, such as websites and work roles) . The announcement is here . There is also a new SharePoint template in the virtual machine image gallery (since you mentioned the use of SharePoint), as well as a SQL Server template.
UPDATE April 30, 2013 . The new 28GB / 56GB sizes are now available with cloud services, which coincides with the release of Azure SDK 2.0 for .NET. More details here .
Just add a little when it comes to web servers: unlike local servers, where it is usually economical to buy the largest machine, it is better to go with smaller virtual machines and have more of them in Windows Azure. So, for a web server, go with the smallest virtual machine that will run your software anyway. Then, to handle additional traffic, scale it to more web instances. As traffic decreases, decrease the number of instances. The load will be distributed among all web servers (which do not have stateless persons - there is no binding of users to a specific instance).
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