Your config file is in a format that the ConvertFrom-StringData can process, which converts lines of =-separated key-value pairs into hashtables:
# Create a sample config.conf file
@'
$CustomerWebUIurl = http://example.org&1
$CustomerSamlIssuerID = http://example.org&2
'@ > ./config.conf
# Load the key-value pairs from ./config.conf into a hashtable:
$config = ConvertFrom-StringData (Get-Content -Raw ./config.conf)
# Output the resulting hashtable
$config
The above yields:
Name Value
---- -----
$CustomerWebUIurl http://example.org&1
$CustomerSamlIssuerID http://example.org&2
That is, $config now contains a hashtable with entries whose key names are - verbatim - $CustomerWebUIurl and $CustomerSamlIssuerID, which you can access as follows: $config.'$CustomerWebUIurl' and $config.'$CustomerSamlIssuerID'
The need to quote the keys on access is somewhat cumbersome, and the fact that the key names start with $ can be confusing, so I suggest defining your config-file entries without a leading $.
If you have no control over the config file, you can work around the issue as follows:
# Trim the leading '$' from the key names before converting to a hashtable:
$config = ConvertFrom-StringData ((Get-Content -Raw .\config.conf) -replace '(?m)^\$')
Now you can access the entries more conveniently as $config.CustomerWebUIurl and $config.CustomerSamlIssuerID