to target elements in the shadow DOM, prefix your css with 
html /deep/
so to target all scrollbars on your site (in webkit browsers like Chrome)
  html /deep/ {
    ::-webkit-scrollbar-track {
      background:white;
    }
    ::-webkit-scrollbar {
      width: 7.5px;
    }
    ::-webkit-scrollbar-thumb {
      background-color: lightgrey; //fallback
      background-color: rgba(26, 26, 26, 0.25);
    }
  }
if you just want to target core-scaffold you can use
  html /deep/ core-scaffold {
    ::-webkit-scrollbar-track {
      background:white;
    }
    ::-webkit-scrollbar {
      width: 7.5px;
    }
    ::-webkit-scrollbar-thumb {
      background-color: lightgrey; //fallback
      background-color: rgba(26, 26, 26, 0.25);
    }
  }
or within the style tags of a custom element (to style only that element)
  :host {
    ::-webkit-scrollbar-track {
      background:white;
    }
    ::-webkit-scrollbar {
      width: 7.5px;
    }
    ::-webkit-scrollbar-thumb {
      background-color: lightgrey; //fallback
      background-color: rgba(26, 26, 26, 0.25);
    }
  }
this answer covers more on shadow DOM styling
you can also use core-style for polymer elements