It's not really clear which part of this you're having problems with. The view models in your library can be registered the same way as any other view model:
SimpleIoc.Default.Register<MainViewModel>();
SimpleIoc.Default.Register<YourClassLibrary.YourClassLibViewModel>();
... etc ...
If your class library has objects that need to be included in the main application resource dictionary (i.e. DataTemplates etc) then put them in a ResourceDictionary just as you normally would do in App.xaml....
<ResourceDictionary xmlns="http://schemas.microsoft.com/winfx/2006/xaml/presentation"
xmlns:x="http://schemas.microsoft.com/winfx/2006/xaml"
xmlns:local="clr-namespace:YourClassLibrary">
<DataTemplate DataType="{x:Type local:YourClassLibViewModel}">
<local:YourClassLibUserControl />
</DataTemplate>
</ResourceDictionary>
...and then add this to your main application's ResourceDictionary's MergedDictionaries
list:
<Application.Resources>
<ResourceDictionary>
<ResourceDictionary.MergedDictionaries>
<ResourceDictionary Source="pack://application:,,,/YourClasssLibrary;component/YourResourceDictionary.xaml" />
</ResourceDictionary.MergedDictionaries>
<vm:ViewModelLocator x:Key="Locator" d:IsDataSource="True" xmlns:vm="clr-namespace:YourMainApp.ViewModel" />
</ResourceDictionary>
</Application.Resources>