Not sure I understand the question. But here's my attempt: Why not create an extractor?
object ValidBigInt {
  def unapply(s: String): Option[Int] = {
    val bi = BigInt(s)
    if (bi.isValidInt) Some(bi.intValue) else None
  }
}
val toInt: PartialFunction[String, Int] = {
  case ValidBigInt(i) => i
}
The other option is (and that may answer the question as to whether one can create PartialFunction other than with a case literal):
val toInt = new PartialFunction[String, Int] {
  def isDefinedAt(s: String) = BigInt(s).isValidInt
  def apply(s: String) = BigInt(s).intValue
}
However since the idea of a partial function is that it's only partially defined, in the end you will still do redundant things -- you need to create a big int to test whether it's valid, and then in the function application you create the big int again...
I saw a project at Github that tried to come around this by somewhat caching the results from isDefinedAt. If you go down to the benchmarks, you'll see that it turned out to be slower than the default Scala implementation :)
So if you want to get around the double nature of isDefinedAt versus apply, you should just go straight for a (full) function that provides an Option[Int] as result.