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I've not found a comprehensive list on anywhere of the PowerShell cmdlets for SharePoint 2013 whose function or output cannot be achieved via the GUI (Central Admin, Site Settings, etc). I would consider these highly important for both IT Pros and Devs.
What are the PowerShell cmdlets that have no GUI equivalent in SharePoint 2013?
The most obvious non-GUI is creating the GUI itself. GUI, in this case, Central Administration, is created via the PowerShell cmdlet New-SPCentralAdministration.
Creating (and most of the maintenance duties for) host named site collections is done entirely in PowerShell. Chapter 1.2
Create the Subscription Settings service, which is needed to enable Apps for SharePoint. New-SPSubscriptionSettingsServiceApplication
Create new proxy groups aren't supported in Central Administration. Instead you need to use the New-SPServiceApplicationProxyGroup cmdlet. Chapter 3.2
Import Signing Certificate for federation between SharePoint and ADFS, is not GUI supported. $signcert = New-Object System.Security.Cryptography.X509Certificates.X509Certificate2("<path to signing cert>") Chapter 2.1
Configure server to server (S2S) trust between two SharePoint farms, SharePoint and Lync or SharePoint and MS Exchange. Chapter 2.1
Reference: Exam Ref 70-331: Core Solutions of Microsoft SharePoint Server 2013
Few which come immediately to mind:
1) Create Host Named Site Collections.
2) Request Management Administration
3) Convert Web Application from Classic Authentication to Claims.
3) Create Web Application with Classic Authentication.
