If your application is a Twitter Client (an app that attempts to replicate Twitter’s core user experience), you will need to contact Platform Operations and potentially obtain approval to exceed 100,000 user tokens.
If your application is not a Twitter Client, then the 100,000 user token limit is likely not applicable to your application. In this case, if you intend to go beyond 1,000,000 user tokens, you’ll need to contact Twitter. It’s likely at those levels you would already be talking to Twitter.
Right now, no matter the situation you think you fall into, the best way to get in contact with Platform Operations/API policy is through https://support.twitter.com/forms/platform