request.headers does not return a hash, but an instance of ActionDispatch::Http::Headers, which is a wrapper around rack env.
ActionDispatch::Http::Headers implements many methods like [] and []= which make it behave like a hash, but it doesn't override the default inspect, hence you can't see the key-value pairs by just p or pp it.
You can, however, see the request headers in the rack env:
pp request.headers.env.select{|k, _| k =~ /^HTTP_/}
Remember that the request headers in rack env are the upcased, underscored and HTTP_ prefixed version of the original http request headers.
UPDATE
Actually there are a finite set of request headers that are not prefixed HTTP_. These (capitalized and underscored) header names are stored in ActionDispatch::Http::Headers::CGI_VARIABLES. I list them below:
AUTH_TYPE
CONTENT_LENGTH
CONTENT_TYPE
GATEWAY_INTERFACE
HTTPS
PATH_INFO
PATH_TRANSLATED
QUERY_STRING
REMOTE_ADDR
REMOTE_HOST
REMOTE_IDENT
REMOTE_USER
REQUEST_METHOD
SCRIPT_NAME
SERVER_NAME
SERVER_PORT
SERVER_PROTOCOL
SERVER_SOFTWARE
So the full version of listing request headers would be
pp request.headers.env.select{|k, _| k.in?(ActionDispatch::Http::Headers::CGI_VARIABLES) || k =~ /^HTTP_/}